JPH07304141A - Package - Google Patents

Abstract

(57) [Summary] [Purpose] To provide various packages excellent in various properties such as strength, transparency, flexibility, and stability against chemicals. [Structure] A polyolefin film composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is used alone or laminated with other layers to form a desired shape into a package.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a package, and more specifically, it has a narrow molecular weight distribution and a very low content ratio of atactic components that are easily extracted by a solvent, and has transparency, aroma retention, flexibility, and low temperature sealing. The present invention relates to a package using a specific polyolefin, which has excellent properties, seal strength, processability, filling machine suitability, and the like, and is excellent in various properties such as little radiation deterioration.

[0002]

2. Description of the Related Art A packaging in which the form of packaging is formed by putting contents therein, that is, flexible packaging (flexible packaging) depends on the strength as a packaging container mainly depending on the size of deformation (spreading) of the packaging material. There is. Therefore,
Flexible sheet-shaped or film-shaped plastics are widely used as packaging materials.

On the other hand, in the packaging of foods, beverages, pharmaceuticals, etc., the performance required of packaging materials is complicated and diversified, and a single material cannot satisfy the requirements.
Laminated films formed by compositing materials having various characteristics are used according to the intended use.

Specifically, for example, packaging materials for foods, beverages, pharmaceuticals, etc., particularly contents to be subjected to pressure heat sterilization, are required to have heat sealability and high barrier property. Conventionally, such a packaging material is, for example, polyethylene terephthalate (PET) in the order of outer layer → inner layer.
/ Stretched nylon (ON) / aluminum (Al) / unstretched polypropylene (CPP) /, polyethylene terephthalate (PET) / aluminum (Al) / unstretched polypropylene (CPP), polyethylene terephthalate (PET) / stretched nylon (ON) / A laminated film having a layered structure such as unstretched polypropylene (CPP) is used.

In the field of tube containers, flexibility, adhesive strength between layers and the like are required, and for example, a laminated film of a heat seal layer made of polyethylene or the like and a barrier layer such as aluminum (Al) foil is used. ing.

Further, in the field of paper containers such as paper cups, since the sealing portion of the container is formed by the heat-welding ability of the laminated film for paper containers, heat-sealing made of a polyolefin resin having high heat-welding ability. Laminated films having layers have been used.

In the field of bag-shaped medical packaging materials such as infusion bags, soft vinyl chloride resins and polyolefin resins are used. In addition, for example, a base material for a medical patch, which is provided with a drug layer such as an anti-inflammatory analgesic, is required to have stability and flexibility with respect to the drug, and thus polyvinyl chloride (P
A laminated film having a VC layer and a urethane resin layer having excellent flexibility is used.

Further, for example, a transparent film used for packaging foods such as processed meat products, processed vegetables products, raw vegetables, and the like, in which fogging occurs due to the water on the surface of the food product and the inside of the food product adhering as water drops. As the anti-fogging film that is prevented, those formed by kneading a surfactant in a resin such as ethylene-vinyl acetate copolymer, high-pressure low-density polyethylene, linear low-density polyethylene, or polypropylene and forming a film are used. Has been.

Polyolefins such as polypropylene, which are conventionally used as materials for forming various packages as described above, are all polymerized using a multisite catalyst having nonuniform active sites. is there.

[0010]

However, for example, in a conventional retort packaging material using polypropylene produced by utilizing the above-mentioned polymerization reaction using a multi-site catalyst, polypropylene has a uniform molecular weight, It contains a large amount of low-molecular components (monomer and low-molecular weight polypropylene) and atactic components with atactic structure, and the content ratio of the components extracted in the solvent is high. Polypropylene polymerized using a multi-site catalyst is used as the innermost layer. When such a conventional packaging material for retort is used for packaging food, such a problem of odor transfer to the contents due to polypropylene arises.

In the case of using polypropylene polymerized by using a multi-site catalyst, a simple substance is not sufficient in terms of physical strength, so a random copolymer with ethylene or a block copolymer is often used. In this case, there is a problem of odor transfer to the contents due to the ethylene component.

Furthermore, when using a retort pouch using polypropylene polymerized with a multi-site catalyst, especially when used in foods containing a large amount of oil components, the polypropylene has a large crystal size and the presence of an ethylene copolymer. Therefore, there are parts with different oil resistance, and after the retort treatment, fine irregularities (so-called citrus skin) occur,
There is a problem that not only the appearance is spoiled, but also the damage to the pouch is great.

Further, in the conventional tube container, there is still room for improvement in the heat-sealing property of the heat-sealing layer formed of polyethylene, for example. On the other hand, in a conventional paper container such as a paper cup, since the polyolefin constituting the laminated film which is the forming material is obtained by the polymerization using the multi-site catalyst, the same as in the case of the retort packaging material. There is a problem of odor transfer to the contents due to such polyolefin, and the low temperature sealing property is not sufficient.

Further, conventional medical packaging materials such as infusion bags have the following problems. That is, since a plastic bag, a stabilizer, and the like are contained in the resin in a medical bag made of a soft vinyl chloride resin, when the liquid medicine such as Ringer solution or glucose solution is stored, these additives are added to the liquid medicine. In addition to elution, there is a problem that a toxic gas is generated when the used bag is incinerated and discarded. On the other hand, in a medical bag made of a polyolefin resin polymerized using a multi-site catalyst, the thickness must be increased in order to obtain sufficient handling strength, and the bag itself becomes hard and inferior in flexibility. Therefore, for example, there is a problem that the liquid drug may not easily come out at the time of infusion. There is also a problem that the transparency is low and it is difficult to see through the state of the liquid drug in the bag.

Further, for example, polyvinyl chloride (PVC)
A conventional medical patch base comprising a laminated film having a layer and a urethane resin layer has a problem that stability and flexibility with respect to a drug are not always sufficient.

Furthermore, conventional anti-fog prepared by kneading a surfactant in a resin such as ethylene-vinyl acetate copolymer, high-pressure low density polyethylene, linear low density polyethylene, polypropylene, etc. and forming a film. The film has a problem that the filling machine suitability such as low temperature sealing property, hot tacking property and sealing strength is not always sufficient.

Therefore, as a result of intensive studies by the present inventors in order to solve such a problem, as a result of using a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst, strength, transparency and flexibility are obtained. The present invention has been accomplished by discovering that various packages having excellent properties such as stability, chemical stability, processability, low-temperature sealing property, hot tack property, and other filling machine suitability can be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is various excellent in various characteristics such as strength, transparency, flexibility, chemical stability, processability, and filling machine suitability. The purpose is to provide a package.

[0019]

[Means for Solving the Problems] In order to achieve the above object, the package of the present invention comprises a polyolefin film comprising a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst, alone or A layer formed by laminating with a layer having a desired shape,
Further, if necessary, the polyolefin is polypropylene, and the innermost layer is a polyolefin layer having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst. A structure formed by molding into a food packaging pouch, and further, if necessary, a structure in which the polyolefin is polypropylene, and a polyolefin composed of a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst. A laminated material having a layer is formed into a tube container, and further, if necessary, the polyolefin is polypropylene, and a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst. A laminated material having a polyolefin layer made of a reolefin is formed into a paper container in which the innermost layer is the polyolefin layer, and if necessary, the polyolefin is made of polypropylene, and a single-site catalyst is also used. A single blank plate consisting of a laminated material having a polyolefin layer consisting of a syndiotactic polyolefin obtained by the polymerization reaction used and containing only the body part is placed in a molding die, and a single-site catalyst is used for this. By injecting the syndiotactic structure polyolefin obtained by the polymerization reaction, the joint gaps, bottoms and openings at both ends of the blank plate are filled with the polyolefin to integrally form a composite container in which the innermost layer is the polyolefin layer. Configured, and if necessary, The composition of the polyolefin is polypropylene, and a composition of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded alone into a medical packaging material, and polymerization using a single-site catalyst is also performed. A laminate material having a polyolefin layer made of a syndiotactic polyolefin obtained by the reaction is formed into a medical packaging material in which the innermost layer is the polyolefin layer, and is obtained by a polymerization reaction using a single-site catalyst. The composition was formed by molding a polyolefin having a syndiotactic structure into a base material for medical patches.

Further, an antifogging film composition obtained by adding one or more surfactants to a syndiotactic polyolefin obtained by a polymerization reaction using a single site catalyst is formed into an antifogging film. If necessary, the composition is such that the addition rate of the surfactant is 0.05 to 5% by weight with respect to 100% by weight of the polyolefin, and if necessary, the antifogging film is laminated on a base film. In addition, the anti-fog film layer and the base film layer formed by adding one or more surfactants to the polyolefin having a syndiotactic structure obtained by the polymerization reaction using a single-site catalyst are extruded and laminated to prevent the formation. The composition is formed by forming a cloudy film, and further, if necessary, the content of the polymer based on 100% by weight of the polyolefin. The composition is such that the addition rate of the surfactant is 0.05 to 5% by weight, and further, the addition rate of the surfactant is 0.05 to 5% by weight with respect to 100% by weight of the polyolefin, or Further, the polyolefin is polypropylene.

[0021]

The package of the present invention is formed into a desired shape by itself or by laminating a polyolefin film composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single site catalyst, or by laminating it with another layer. It will be. The polyolefin of syndiotactic structure obtained by the polymerization reaction using this single site catalyst, especially polypropylene, has a narrow molecular weight distribution, the content ratio of the atactic component that is easily extracted in the solvent is extremely low, the spherulite size is small, and radiation deterioration is caused. Low temperature sealability,
It has excellent properties such as hot tack, seal strength, flexibility, transparency, surface gloss and cold shock resistance. Therefore, in a package formed by molding such a polyolefin, especially a laminated composite material obtained by laminating polypropylene with other layers into a pouch for food packaging, there is no odor transfer to the contents, and retort treatment is performed. However, fine irregularities (so-called citrus skin) do not occur on the surface. Further, a package formed by molding a laminated composite material obtained by laminating such a polyolefin, particularly polypropylene with other layers, into a tube container has a good squeeze property, is easy to squeeze out the contents, and is transferred to the contents. It is odorless and has excellent transparency, surface gloss and cold shock resistance. In addition, a package formed by molding such a polyolefin, particularly a laminated composite material obtained by laminating polypropylene with another layer, into a paper container having the polyolefin layer as the innermost layer has excellent sealing strength and aroma retention. It is excellent and does not transfer odor to the contents. Also, one blank plate composed of a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst and containing only a body part is placed in a molding die, A package formed by integrally injecting a syndiotactic structure polyolefin into a composite container in which the joining gaps, bottoms and openings at both ends of the blank plate are filled with the polyolefin and the innermost layer is the polyolefin layer. Has excellent strength and excellent fragrance retention, and does not transfer odor to the contents. In addition, the package formed by molding the syndiotactic structure polyolefin obtained by the polymerization reaction using the single-site catalyst into the medical packaging material alone is excellent in transparency and easy to see through the contents and flexibility. There is no problem that the liquid drug, which is the content, is hard to come out at the time of infusion, and the strength does not deteriorate even if sterilization treatment is performed by irradiation with radiation. Further, a package formed by molding a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into a medical packaging material in which the innermost layer is the polyolefin layer is stable against drugs. It has excellent properties and does not deteriorate in strength even if it is sterilized by irradiation. Further, a package formed by molding a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst into a laminated sheet for medical patch is excellent in stability against a drug and is flexible.
Furthermore, a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst,
In particular, the packaging formed by using polypropylene to form an anti-fog film has excellent transparency, has a very low content of low-molecular weight substances, and has a low content of high-crystallinity polyolefin chains. Not only is it excellent, but it is also superior in low-temperature sealability, hot tackiness, and seal strength compared to the conventional isotactic polyolefin obtained by the polymerization reaction using the Ziegler-Natta catalyst. Therefore, a package formed by molding a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst into an anti-fog film has both excellent anti-fog properties and good filling machine suitability.

Here, the single-site catalyst (including a metallocene catalyst, a so-called Kaminsky catalyst) is characterized in that the active sites are uniform (single site). This single-site catalyst is a catalyst composed of a metallocene-based transition metal compound and an organic aluminum compound, and may be used by being supported on an inorganic substance.

Here, as the metallocene-based transition metal compound, for example, a transition metal selected from Group IVB, that is, titanium (Ti), zirconium (Zr), hafnium (Hf), a cyclopentadienyl group and a substituted cyclopenta group are used. Dienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group has 1 to 2 bonds, or two of these groups are covalent bonds. The crosslinked ones are bonded, and other hydrogen atoms,
Oxygen atom, halogen atom, alkyl group, alkoxy group,
Aryl group, acetylacetonato group, carbonyl group,
Examples thereof include those having a ligand such as a nitrogen molecule, an oxygen molecule, a Lewis base, a substituent containing a silicon atom, and an unsaturated hydrocarbon.

Further, as the organoaluminum compound,
Examples thereof include alkyl aluminum, chain-like or cyclic aluminoxane, and the like. Here, as the alkylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminium chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminium fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like can be mentioned. Can be mentioned.

The chain or cyclic aluminoxane is produced by bringing alkylaluminum into contact with water. For example, it can be obtained by adding alkylaluminum at the time of polymerization and then adding water, or by reacting water of crystallization of a complex salt or adsorbed water of an organic / inorganic compound with alkylaluminum.

Examples of the inorganic material carrying the single-site catalyst include silica gel, zeolite, diatomaceous earth and the like. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization and gas phase polymerization. Further, these polymerizations may be either batch type or continuous type.

The polymerization conditions are as follows. That is,
The polymerization temperature is usually about -100 ° C to 250 ° C,
The polymerization time is usually about 5 minutes to 10 hours, and the reaction pressure is usually atmospheric pressure to about 300 kg / cm ² .

Examples of the monomer used in the polymerization using such a single-site catalyst include propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1- Examples include α-olefins such as octene and decene. These α-olefins may be used alone or in combination of two or more. Of these, propylene is particularly preferable.

The polyolefin obtained by the polymerization reaction using a single-site catalyst includes, for example, antioxidants, ultraviolet absorbers, antistatic agents, antiblocking agents, flame retardants, inorganic and organic fillers, dyes. , Pigments and the like can be appropriately added as needed.

The stereochemical structure of the polyolefin obtained by polymerization using a single site catalyst as described above has a syndiotactic structure. Here, the syndiotactic structure refers to a structure in which an alkyl group or a substituted alkyl group, which is a side chain, is alternately located in the half direction with respect to the main chain.

It is difficult to uniformly determine the syndiotacticity of this syndiotactic structure polyolefin because of the high degree of freedom by the catalyst, but it is preferably at least 70%.

Among these polyolefins, polypropylene is particularly preferable, and its physical properties are, for example, molecular weight distribution Mw / Mn = 1.5 to 3, density: 0.88 (g / cm ³ ), Melt index [M
I]: 1.5 to 20.

[0033]

EXAMPLES Next, examples of the present invention will be shown to more specifically describe the package of the present invention. First Example An experimental example in the case where a pouch for food packaging is made by using a laminated material having a polyolefin layer made of a polyolefin obtained by a polymerization reaction using a single-site catalyst is shown below. -Experimental Example 1-In order from the outermost layer to the innermost layer, a polyethylene terephthalate (PET) layer [thickness 12 µm] / drawn nylon (ON)
Layer [thickness 15 μm] / aluminum (Al) layer [thickness 7
μm] / Polypropylene layer of syndiotactic structure polymerized using a single-site catalyst [thickness 70 μm]
A packaging material for a retort was prepared by laminating each layer of (Syndiotacticity: 0.81) using a urethane adhesive, and a three-sided bag of 150 mm x 180 mm was made into a pouch. The single-site catalyst contains zirconocene dichloride and methylalumoxane in a molar ratio of 1: 1.
The combined catalyst was used in a ratio of 250.

The pouch was filled with water and the temperature was 120 ° C.
It was sterilized by heating under pressure (retort) for 30 minutes, and the smell of water as a content was sensory evaluated. The results are shown in Table 1.

[0035]

[Table 1] In addition, after retort, 10 bags of pouches stored at a temperature of 3 ° C for 1 week or more were subjected to a drop test up to 30 times with the surface heat-sealed last from the height of 120 cm to the limit of 30 times. The average bag breakage rate was calculated. The results are shown in Table 2.

Average bag breakage rate = (number of broken bag samples) /
[Number of times required to break the bag (30 times if the bag is not broken within 30 times)]

[0037]

[Table 2] Next, the pouch was filled with a commercially available curry and the temperature was adjusted to 12
The pouch surface was observed by performing pressure heat sterilization at 0 ° C. for 30 minutes. The results are shown in Table 3.

[0038]

[Table 3] -Comparative Example 1-A pouch was prepared in the same manner as in Experimental Example 1 except that the innermost layer was a homopolypropylene layer made of polypropylene polymerized using a multisite catalyst. After that, the sensory evaluation of the odor of water was performed in the same manner as in Experimental Example 1, the average bag-breaking rate in the drop test was calculated, and the pouch surface after pressure heat sterilization with curry filled was used. I observed. The respective results are shown in Tables 1 to 3. -Comparative Example 2-A pouch was prepared in the same manner as in Experimental Example 1 except that the innermost layer was a random copolymer layer of propylene and ethylene polymerized by using a multisite catalyst. After that, the sensory evaluation of the odor of water was performed in the same manner as in Experimental Example 1, the average bag-breaking rate in the drop test was calculated, and the pouch surface after pressure heat sterilization with curry filled was used. I observed. The respective results are shown in Tables 1 to 3. -Comparative Example 3-A pouch was prepared in the same manner as in Experimental Example 1 except that the innermost layer was a block copolymer layer of propylene and ethylene polymerized by using a multisite catalyst. After that, the sensory evaluation of the odor of water was performed in the same manner as in Experimental Example 1, the average bag-breaking rate in the drop test was calculated, and the pouch surface after pressure heat sterilization with curry filled was used. I observed. The respective results are shown in Tables 1 to 3. -Study of Results- As is clear from Table 1, in the pouches of Comparative Examples 1 to 3 (conventional products), the content of water caused a polyodor, whereas the synergies polymerized using a single-site catalyst were used. In the pouch of Experimental Example 1 in which polypropylene having an tactic structure was used as the innermost layer, no polyodor was generated from the water content.

Further, as is clear from Table 2, the pouches of Experimental Example 1 in which polypropylene having a syndiotactic structure polymerized by using a single-site catalyst is the innermost layer are the pouches of Comparative Examples 1 to 3 (conventional). It was confirmed that the average bag-breaking rate was equal to or higher than that of the product).

Further, in the pouch of Experimental Example 1 in which polypropylene having a syndiotactic structure polymerized by using a single site catalyst was used as the innermost layer, the surface was smooth even after the retort treatment of the food containing a large amount of oil components. ,
The occurrence of yuzu skin as in Comparative Examples 2 and 3 was not observed.

From the above results, it can be seen that the pouch for food packaging of this example has no odor to the contents, has sufficient strength, and does not cause yuzu. Second Example The following is an experimental example in which a tube container is formed using a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst. -Experimental Example 2-Polypropylene layer having a syndiotactic structure polymerized using a single-site catalyst in order from the outermost layer to the innermost layer (containing 0.05% by weight of talc, syndiotacticity: 0.81, melt index [ MI]: 3.2,
Density 0.88 g / cm ³ ) / Adhesive layer (maleic anhydride-modified polypropylene) / Oxygen barrier resin layer [Ethylene-vinyl alcohol copolymer resin layer (ethylene content 30
Mol%, vinyl alcohol content 69.7 mol%, vinyl acetate content 0.3 mol%)] / adhesive layer (maleic anhydride modified polypropylene) / polypropylene having a syndiotactic structure polymerized using a single site catalyst Layer (containing 0.05% by weight of talc, syndiotacticity: 0.81, melt index [MI]: 3.2,
The density is 0.88 g / cm ³ ) and the thickness ratio of (outermost layer) :( adhesive layer) :( oxygen barrier resin layer) :( adhesive layer) :( innermost layer) is 3.3: 0. 6: 1: 0.6: 3.
In Fig. 1, a tube formed by stacking 3 types and 5 layers is extruded so that the thickness becomes 0.25 mm (average thickness of the body portion) in Fig. 3.
The tube container 1 shown in was prepared. This tube container 1
Was evaluated for haze, surface gloss and extrusion properties. The results are shown in Table 4.

[0042]

[Table 4] The evaluation method for each item is as follows. Haze: Haze of the shoulder was measured and evaluated as a percentage (%).

Surface gloss: The surface gloss of the shoulder was measured at θ = 60 ° and evaluated as a percentage (%). Extrusion characteristics: A tube container filled with toothpaste is placed horizontally with the cap removed, and a flat plate is pressed from the bottom side of the tube toward the neck to push out the toothpaste, and the extrusion amount is a percentage of the total filling amount. (%) Evaluated.

Next, the mouth portion of a tube container similar to that described above is provided with polyethylene terephthalate (PE) in order from the outer layer to the inner layer.
T) A three-layer laminated film consisting of [thickness 12 μm] / aluminum foil (thickness 35 μm) / modified polypropylene (easy peeling layer) [thickness 50 μm] was heat-sealed and filled with pure water. After degassing and sealing, retort sterilization treatment was performed at 120 ° C. for 30 minutes, and a sensory test was performed on the water in the treated tube. The results are shown in Table 5.

[0045]

[Table 5] -Comparative Example 4- In Experimental Example 2, a laminated material of 3 types and 5 layers consisting of a syndiotactic polyproprene layer / adhesive layer / oxygen barrier resin layer / adhesive layer / syndiotactic polypropylene layer Instead of, isotactic polypropylene homopolymer layer polymerized using multisite catalyst / adhesive layer / oxygen barrier resin layer / adhesive layer / isotactic polypropylene homopolymer polymerized using multisite catalyst 3 kinds of layers 5
A tube container was prepared in the same manner as in Experimental Example 2 except that the layered material was used, and the haze, surface gloss, and extrusion characteristics of the tube container were evaluated in the same manner as in Experimental Example 2. A sensory test was performed on the water filled in this tube container after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Comparative Example 5- In Experimental Example 2, a laminated material of three types and five layers including a syndiotactic structure polypropylene layer / adhesive layer / oxygen barrier resin layer / adhesive layer / syndiotactic structure polypropylene layer. Instead of, a random copolymer layer of polypropylene and ethylene having an isotactic structure polymerized using a multisite catalyst / adhesive layer / oxygen barrier resin layer / adhesive layer / isotactic structure polymerized using a multisite catalyst A tube container was prepared in the same manner as in Experimental Example 2 except that the laminated material of 5 types of 3 types consisting of the random copolymer layer of polypropylene and ethylene was used, and the tube container was prepared in the same manner as in Experimental Example 2 above. The haze, surface gloss, and extrusion properties were evaluated and the tube container was filled. A sensory test was performed on water after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Comparative Example 6-In Experimental Example 2, a laminated material of 3 types and 5 layers including a polyproprene layer having a syndiotactic structure / adhesive layer / oxygen barrier resin layer / adhesive layer / a polypropylene layer having a syndiotactic structure. Instead of, a block polymer layer of polypropylene and ethylene having an isotactic structure polymerized using a multisite catalyst / adhesive layer / oxygen barrier resin layer / adhesive layer / isotactic structure polymerized using a multisite catalyst A tube container was prepared in the same manner as in Experimental Example 2 except that the layered material of 3 types and 5 layers consisting of the block polymer layer of polypropylene and ethylene was used.
Each of haze, surface gloss and extrusion characteristics was evaluated in the same manner as in, and a sensory test was performed on the water filled in the tube container after the retort sterilization treatment.
The respective results are shown in Tables 4 and 5. -Experimental Example 3-A polypropylene film composed of polypropylene having a syndiotactic structure polymerized using a single-site catalyst in order from the outermost layer to the innermost layer (syndiotacticity: 0.81, melt index [MI]: 3. 2,
Density 0.88 g / cm ³ ) [thickness 100 μm], polyethylene terephthalate film [thickness 12 μm], stretched nylon film [thickness 25 μm], and polypropylene film of syndiotactic structure polymerized using a single-site catalyst (Syndi) Geek City: 0.
81, melt index [MI]: 3.2, density 0.
88 g / cm ³ ) [thickness 100 μm] is dry laminated with a urethane-based adhesive to form a laminated material, which is formed into a tubular shape by high-frequency sealing, and has the same syndiotactic structure as the outermost layer and the innermost layer. A tube container 1'shown in FIG. 2 was prepared by integrally molding the shoulder portion by injection processing using the polypropylene film of No. 1, and the tube container 1'was used in Experimental Example 2 described above.
Each of the haze and the surface gloss was evaluated in the same manner as in, and a sensory test was performed on the water filled in the tube container after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Comparative example 7-In the said Experimental example 3, it replaced with the polypropylene film which consists of polypropylene of a syndiotactic structure polymerized using the single site catalyst, The polypropylene homopolymer of the isotactic structure polymerized using a multi site catalyst. Except that the polypropylene film consisting of was used, a laminated material was prepared and a tube container was prepared in the same manner as in Experimental Example 3, and the haze and surface gloss of each of the tube containers were evaluated in the same manner as in Experimental Example 3. At the same time, a sensory test was performed on the water filled in the tube container after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Comparative Example 8- In the above-mentioned Experimental Example 3, instead of the polypropylene film made of polypropylene having a syndiotactic structure polymerized by using a single site catalyst, polypropylene and ethylene having an isotactic structure polymerized by using a multisite catalyst were used. A laminate material and a tube container were prepared in the same manner as in Experimental Example 3 except that the random copolymer film with was used, and the haze and the surface gloss of the tube container were measured in the same manner as in Experimental Example 3. In addition to the evaluation, a sensory test was performed on the water filled in this tube container after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Comparative Example 9-In Experimental Example 3, instead of the polypropylene film made of polypropylene having a syndiotactic structure polymerized using a single site catalyst, polypropylene and ethylene having an isotactic structure polymerized using a multisite catalyst were used. Except that the block copolymer film of and was used, a laminated material was prepared and a tube container was prepared in the same manner as in Experimental Example 3, and the haze and the surface gloss of the tube container were measured in the same manner as in Experimental Example 3. In addition to the evaluation, a sensory test was performed on the water filled in this tube container after the retort sterilization treatment. The respective results are shown in Tables 4 and 5. -Examination of Results- From Table 4, the tube containers of Experimental Examples 2 and 3 (invention products) are superior in haze and surface gloss to the tube containers of Comparative Examples 4 to 9 (conventional product), and also in Experimental Examples. It can be seen that the tube container of No. 2 (product of the present invention) has excellent extrusion characteristics as compared with the tube containers of Comparative Examples 4 to 6 (conventional product).
Furthermore, from Table 5, none of the tube containers of Experimental Examples 2 and 3 (product of the present invention) had odor migration to the contents, and the fragrance retention was higher than that of the tube containers of Comparative Examples 4 to 9 (conventional product). It turns out to be excellent. Third Example The following is an example of an experiment in which the layered material having a polyolefin layer made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is used to form the Gobeltop paper container 2 shown in FIG. Show. -Experimental example 4- First, one side of paper (basis weight 340g / m < ² >) was coated with low density polyethylene (LDPE) by the extrusion method, and the laminated material of paper and low density polyethylene (LDPE) was created.

Next, this laminated material and aluminum (Al)
A foil and a foil are laminated by a PE sand method, and biaxially oriented polyester (O-PE
T) and a polypropylene having a syndiotactic structure polymerized using a single-site catalyst (syndiotacticity: 0.81, melt index [MI]:
3.2, density 0.88 g / cm ³ ) was dry-laminated with a urethane-based adhesive, and then printing was performed on the low-density polyethylene (LDPE) layer side to prepare a laminated material having the following structure. The following configurations are shown in order from the outermost layer to the innermost layer.

Printing Layer / Low Density Polyethylene (LDPE)
[Thickness 20 μm] / paper (basis weight 340 g / m ² ) / low density polyethylene (LDPE) [thickness 30 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / biaxially stretched polyester (O-PET) ) [Thickness 12 μm] / adhesive layer / polypropylene having a syndiotactic structure [thickness 60 μm
m] Next, a rectangular blank was punched out from this laminated material, and a Goebel top type paper container having a capacity of 1000 ml was prepared according to a conventional method.

1000 parts mineral water in this paper container
After filling with ml and storing at 10 ° C. for 2 weeks, the flavor of mineral water was sensory evaluated. The results are shown in Table 6.

[0049]

[Table 6] -Experimental Example 5- First, one side of paper (basis weight: 340 g / m < ² >) was coated with low density polyethylene (LDPE) by an extrusion method to prepare a laminated material of paper and low density polyethylene (LDPE).

Next, a polypropylene having a syndiotactic structure was polymerized on the paper side of this laminated material using a single site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0). 0.88 g / c
m ³ ) by the extrusion method, and then
Printing was performed on the low-density polyethylene (LDPE) layer side to prepare a laminated material having the following structure. The following configurations are shown in order from the outermost layer to the innermost layer.

Printing Layer / Low Density Polyethylene (LDPE)
[Thickness 20 μm] / paper (basis weight 340 g / m ² ) / polypropylene having a syndiotactic structure [thickness 35 μm] Thereafter, a Gobeltop paper container was prepared in the same manner as in Experimental Example 4, and the flavor of mineral water was added. Was sensory evaluated. The results are shown in Table 6. -Comparative Example 10- First, one side of paper (basis weight: 340 g / m < ² >) was coated with low density polyethylene (LDPE) by an extrusion method to prepare a laminated material of paper and low density polyethylene (LDPE). Next, this laminated material and aluminum (Al)
A foil and a foil are laminated by the PE sand method, and biaxially oriented polyester (O-PE) is further applied to the aluminum (Al) foil side.
T) is dry-laminated with a urethane adhesive, corona discharge treatment is further applied to this O-PET surface, and low density polyethylene (LDPE) is laminated by PE sand method, and then low density polyethylene (LDPE) layer side Was printed on to prepare a laminated material having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Printing Layer / Low Density Polyethylene (LDPE)
[Thickness 20 μm] / paper (basis weight 340 g / m ² ) / low density polyethylene (LDPE) [thickness 30 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / biaxially stretched polyester (O-PET) ) [Thickness 12 μm] / Low-density polyethylene (LDPE) [Thickness 20 μm] / Low-density polyethylene (LDPE) [Thickness 40 μm] Thereafter, in the same manner as in Experimental Example 4, a Gabeltop paper container was prepared, and mineral water was prepared. The sensory evaluation of the flavor of The results are shown in Table 6. -Comparative Example 11- First, both sides of paper (basis weight 340 g / m < ² >) were coated with low density polyethylene (LDPE) by an extrusion method to prepare a laminated material of paper and low density polyethylene (LDPE).

Next, one side of this laminated material was subjected to corona discharge treatment and then printed to prepare a laminated material having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer. Printed layer / Low density polyethylene (LDPE) [Thickness 20μ
m] / paper (basis weight 340 g / m ² ) / low density polyethylene (LDPE) [thickness 35 μm] Thereafter, a Gobeltop paper container was prepared in the same manner as in Experimental Example 4, and the flavor of mineral water was sensory evaluated. . The results are shown in Table 6. -Examination of Results- From Table 6, all of the Gabeltop paper containers (invention products) of Experimental Examples 4 and 5 have no odor to the contents and Comparative Examples 10 to 1
It can be seen that the fragrance retaining property is superior to that of the No. 1 gobel top type paper container (conventional product). Fourth Example The following is an example of an experiment in which the paper cup 3 shown in FIG. 3 is made by using a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst. -Experimental Example 6-First, printing is performed on one side of paper (basis weight: 280 g / m ² ),
Polypropylene composed of polypropylene having a syndiotactic structure polymerized on its printed surface using a single site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0.88 g / cm 3
³ ) was coated by the extrusion method to prepare a laminated material of paper and polypropylene of syndiotactic structure.

Next, this laminated material and aluminum (Al)
A foil and a foil are laminated by the PE sand method, and biaxially oriented polyester (O-PE) is further applied to the aluminum (Al) foil side.
T) and a polypropylene having a syndiotactic structure polymerized using a single-site catalyst (syndiotacticity: 0.81, melt index [MI]:
3.2, density 0.88 g / cm ³ ) was dry-laminated with a urethane adhesive to prepare a laminated material for a body having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Polypropylene of syndiotactic structure [thickness 20 μm] / printing layer / paper (basis weight: 280 g / m ² ).
/ Low-density polyethylene (LDPE) [thickness 30 μm] /
Aluminum (Al) foil [thickness 9 μm] / adhesive layer / biaxially oriented polyester (O-PET) [thickness 15 μm] / adhesive layer / polypropylene with syndiotactic structure [thickness 80 μm] On the other hand, for the body A bottom laminated material having the following structure was prepared according to the preparation of the laminated material. The following configurations are shown in order from the outermost layer to the innermost layer.

Syndiotactic polypropylene [thickness 20 μm] / paper (basis weight 230 g / m ² ) low density polyethylene (LDPE) [thickness 30 μm] / aluminum foil [thickness 9 μm] / adhesive layer / biaxial stretching Nylon (ON
y) [thickness 12 μm] / adhesive layer / polypropylene having syndiotactic structure [thickness 80 μm] Then, a paper cup was prepared according to a conventional method using these laminated materials for the body and the bottom. The body was subjected to skive hemming.

Mineral water 180 in this paper cup
ml was filled, and the same laminate material as the bottom laminate material was used as a lid material and heat-sealed. After storing this at 10 ° C. for 2 weeks, the flavor of mineral water was sensory evaluated. The results are shown in Table 7.

[0058]

[Table 7] -Comparative Example 12- First, printing is performed on one side of paper (basis weight: 280 g / m < ² >),
Polypropylene composed of polypropylene having a syndiotactic structure polymerized on its printed surface using a single site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0.88 g / cm 3
³ ) was coated by the extrusion method to prepare a laminated material of paper and polypropylene of syndiotactic structure. Next, this laminated material and an aluminum (Al) foil are laminated by a PE sand method, and biaxially stretched polyester (O-PET) is dry-laminated on the aluminum (Al) foil side with a urethane adhesive. Low density polyethylene (LDPE) was dry-laminated on the O-PET surface with a urethane-based adhesive to prepare a laminated material for a body having the following structure. The following configurations are shown in order from the outermost layer to the innermost layer.

Low density polyethylene (LDPE) [thickness 2
0 μm] / printing layer / paper (basis weight 280 g / m ² ) / low density polyethylene (LDPE) [thickness 30 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / biaxially oriented polyester (O-PET) ) [Thickness 12 μm] / Adhesive layer / Low-density polyethylene (LDPE) [Thickness 80 μm] On the other hand, a bottom laminated material having the following constitution was prepared according to the above-mentioned preparation of the laminated material for the body. The following configurations are shown in order from the outermost layer to the innermost layer.

Low density polyethylene (LDPE) [thickness 2
0 μm] / printing layer / paper (basis weight 230 g / m ² ) / low density polyethylene (LDPE) [thickness 30 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / biaxially stretched nylon (ONy) [ Thickness 15 μm / adhesive layer / low density polyethylene (LDPE) [thickness 80 μm] Thereafter, a paper cup was prepared in the same manner as in Experimental Example 6, and the flavor of mineral water was sensory evaluated. The results are shown in Table 7. -Experimental Example 7-First, printing is performed on one side of paper (basis weight: 280 g / m ² ),
Polypropylene composed of polypropylene having a syndiotactic structure polymerized on both sides with a single-site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0.88 g / c
m ³ ) was coated by an extrusion method to prepare a laminated material for body having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Polypropylene of syndiotactic structure [thickness 20 μm] / printing layer / paper (basis weight: 280 g / m ² ).
/ Polypropylene with syndiotactic structure [Thickness 40
μm] On the other hand, a bottom laminated material having the following structure was prepared according to the above-described preparation of the body laminated material. The following configurations are shown in order from the outermost layer to the innermost layer.

Polypropylene of syndiotactic structure [thickness 20 μm] / paper (basis weight: 230 g / m ² ) / polypropylene of syndiotactic structure [thickness 40 μm] After that, except that no skive hemming treatment was applied to the body A paper cup was prepared in the same manner as in Experimental Example 6, and the flavor of mineral water was sensory evaluated. The results are shown in Table 7. -Experimental Example 8- First, printing is performed on one side of paper (basis weight: 280 g / m < ² >),
Polypropylene composed of polypropylene having a syndiotactic structure polymerized on the opposite surface using a single-site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0.88 g /
cm ³ ) was coated by an extrusion method to prepare a laminated body material for body having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Printed layer / paper (basis weight: 280 g / m ² ) / polypropylene having a syndiotactic structure [thickness: 40 μm] On the other hand, according to the above-mentioned preparation of the laminated material for the body, the laminated material for the bottom having the following constitution It was created. The following configurations are shown in order from the outermost layer to the innermost layer.

Paper (basis weight: 230 g / m ² ) / polypropylene having a syndiotactic structure [thickness: 40 μm] A paper cup was prepared in the same manner as in Experimental Example 6 except that the body was not subjected to skive hemming. The sensory evaluation of the flavor of mineral water was carried out. The results are shown in Table 7. -Comparative Example 13- First, printing is performed on one side of paper (basis weight: 280 g / m < ² >),
Low density polyethylene (LDPE) was coated on the opposite surface by an extrusion method to prepare a laminated material for a body having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Printing layer / paper (basis weight: 280 g / m ² ) / low-density polyethylene (LDPE) [thickness: 40 μm] On the other hand, the bottom laminated material having the following constitution in accordance with the above-mentioned preparation of the laminated material for the body It was created. The following configurations are shown in order from the outermost layer to the innermost layer.

Paper (basis weight: 230 g / m ² ) / low-density polyethylene (LDPE) [thickness: 40 μm] Thereafter, a paper cup was prepared in the same manner as in Experimental Example 6 except that the body was not skived and hemmed. Then, the flavor of the mineral water was sensory evaluated. The results are shown in Table 7. -Examination of Results- From Table 7, the paper cups of Experimental Examples 6 to 8 (invention products) all had no odor to the contents, and exhibited aroma retention compared to the paper cups of Comparative Examples 12 and 13 (conventional products). It turns out to be excellent. Fifth Example A single blank plate made of a laminated material having a polyolefin layer made of a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst and having only a body portion was placed in a molding die. By injecting the syndiotactic structure polyolefin obtained by the polymerization reaction using a single-site catalyst, the joint gaps, bottoms and openings at both ends of the blank plate are filled with the syndiotactic structure polyolefin. An example of an experiment in which the inner layer is integrally molded with the composite container 4 shown in FIG. 4 in which the polyolefin has a syndiotactic structure is shown below. -Experimental Example 9- First, paper (basis weight: 280 g / m < ² >) and biaxially oriented polyester (O-PET) with printing on one side are laminated by the PE sand method so that the printing surface is on the paper side. Then, the paper surface and an aluminum (Al) foil were laminated by the PE sand method. Next, a polypropylene film (syndiotacticity: 0.81, melt index [MI]: 3.2) made of polypropylene having a syndiotactic structure polymerized on the aluminum (Al) foil surface using a single-site catalyst. , Density 0.88 g / cm ³ ) was dry-laminated using a urethane adhesive to prepare a laminated material having the following constitution. The following configurations are shown in order from the outermost layer to the innermost layer.

Biaxially oriented polyester (O-PET) [thickness 12 μm] / printing layer / low density polyethylene (LDP)
E) [thickness 15 μm] / paper (basis weight 280 g / m ² ) / low density polyethylene (LDPE) [thickness 15 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / polypropylene with syndiotactic structure [Thickness 60 μm] Next, the above-mentioned laminated material was punched into a so-called blank shape in which a body portion and a bottom portion were connected to each other to form a blank plate, and the blank plate was arranged between the core of the injection molding die and the female die. . Then, a polypropylene having a syndiotactic structure was polymerized in the mold using a single site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0.88 g / cm ³ ). By injecting, the polypropylene having the syndiotactic structure forming the innermost layer of the blank plate and the injected polypropylene having the syndiotactic structure were fused to form a cup-shaped composite container (pillar pack). .

180 mineral water in this composite container
ml was filled, and the same laminated material as that used for the blank plate was heat-sealed as a lid material. After storing this at 10 ° C. for 2 weeks, the flavor of mineral water was sensory evaluated. The results are shown in Table 8.

[0069]

[Table 8] -Comparative Example 14- First, paper (basis weight: 280 g / m < ² >) and biaxially stretched polyester (O-PET) with printing on one side are laminated by a PE sand method so that the printing surface faces the paper side. Then, the paper surface and an aluminum (Al) foil were laminated by the PE sand method. Next, an atactic polypropylene unstretched polypropylene (CPP) film polymerized on the aluminum (Al) foil surface using a multi-site catalyst was dry-laminated using a urethane-based adhesive to obtain a laminated material having the following structure. Created. The following configurations are shown in order from the outermost layer to the innermost layer.

Biaxially oriented polyester (O-PET) [thickness 12 μm] / printing layer / low density polyethylene (LDP)
E) [thickness 15 μm] / paper (basis weight 280 g / m ² ) / low density polyethylene (LDPE) [thickness 15 μm] / aluminum (Al) foil [thickness 9 μm] / adhesive layer / unstretched polypropylene (CPP) [Thickness 60 μm] Next, the above-mentioned laminated material was punched into a so-called blank shape in which a body portion and a bottom portion were connected to each other to form a blank plate, and the blank plate was arranged between the core of the injection molding die and the female die. . Then, by injecting polypropylene of atactic structure polymerized using a multisite catalyst in this mold, a non-stretched atactic structure of atactic structure polymerized using a multisite catalyst that constitutes the innermost layer of the blank plate A cup-shaped composite container (pillar pack) in which polypropylene and injected polypropylene with an atactic structure were fused and integrated together.

180 minutes mineral water in this composite container
ml was filled, and the same laminated material as that used for the blank plate was heat-silled as a lid material. 2 at 10 ℃
After storage for a week, the flavor of mineral water was sensory evaluated. The results are shown in Table 8. —Examination of Results— As is clear from Table 8, the flavor of mineral water is good in the composite container of Experimental Example 9 (product of the present invention), while the mineral water is good in the composite container of Comparative Example 14 (product of the present invention). The flavor of the water was poor. From this, it was confirmed that the composite container of the present invention is superior in aroma retaining property as compared with the conventional composite container. Sixth Example A polyolefin film made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst was formed into a bag shape, for example, storage of a liquid drug such as Ringer's solution or glucose solution, or artificial dialysis. An example of an experiment in the case of a medical bag that can be suitably used for containing a waste liquid at that time is shown below. -Experimental Example 10- Thickness 2 made of polypropylene having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst
A polypropylene bag of 50 μm was used and heat sealing was carried out on all sides except for the filling port of the content, to obtain a flexible medical bag having a capacity of 200 ml.

Then, this medical bag was filled with Ringer's solution, and the filling port was heat-sealed to seal it.
Retort sterilization treatment was performed at 120 ° C for 30 minutes. When this medical bag was subjected to transparency, appearance, water vapor permeation test, heavy metal elution test, and ignition residue elution test according to the Japanese Pharmacopoeia “Infusion Plastic Container Test Method”, all cleared the standards. Was confirmed. Further, when this medical bag was subjected to a drop test from a height of 1.8 m, no bag was broken and the strength of the seal portion was sufficient. Seventh Example A polyolefin film comprising a syndiotactic polyolefin obtained by a polymerization reaction using a single-site catalyst was used to mold a lid material for a medical container,
For example, an experimental example in the case of a medical container that can be suitably used for storing an injection needle, a vacuum blood collection tube, etc. will be shown below. -Experimental Example 11- Thickness 1 made of polypropylene having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst
A 50 μm polypropylene film was used as an easy-peel lid material for a polypropylene tray container for a vacuum blood collection tube, and a polypropylene tray container whose opening was covered with the lid material was prepared.

Then, the tray container was subjected to sterilization treatment by γ-ray irradiation. As a result, a medical container having little strength deterioration after γ-ray irradiation was obtained. This medical container is γ
Even after irradiation with rays, it had good easy peeling suitability, and no problems such as tearing of the lid material during peeling occurred. Eighth Example An example of an experiment in which a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst is molded into a laminated sheet for medical patch is shown below. -Experimental Example 12-Polypropylene having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst (syndiotacticity: 0.81, melt index [M
I]: 3.2, a density of 0.88 g / cm ³ ) as a base material, a polypropylene film having a thickness of 50 μm, and an adhesive layer formed by kneading an acrylic resin with a chemical agent is formed on one side of the polypropylene film. Further, a release film made of a PET film having one surface subjected to silicone release treatment was laminated on the pressure-sensitive adhesive layer surface to obtain a laminated sheet for medical patch having the following layer structure.

Polypropylene / adhesive layer / releasing film having syndiotactic structure The laminate sheet for medical patch was subjected to a sensory evaluation of flexibility and aroma retention,
The laminated sheet for medical patch was highly flexible, and the chemical odor was not felt so much. -Comparative Example 15-In Experimental Example 12, polypropylene having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst (syndiotacticity: 0.81, melt index [MI]: 3.2, density 0) .88 g /
Instead of polypropylene film having a thickness of 50μm consisting of cm ^3), a thickness of 50μm polyvinyl chloride (PVC)
A laminated sheet for medical patch was prepared in the same manner as in Experimental Example 12 except that the film was used.

Regarding the laminated sheet for medical patch,
When a sensory evaluation of flexibility and aroma retention was conducted in the same manner as in Experimental Example 12, the flexibility was poor and the chemical odor was strong. -Examination of Results-From the results of Experimental Example 12 and Comparative Example 15, the laminated sheet for medical patches (invention product) using the syndiotactic structure polypropylene obtained by the polymerization reaction using a single-site catalyst was as follows: It can be seen that, as compared with a laminated sheet for medical patches (conventional product) using a laminated film of polyvinyl chloride (PVC) and a urethane resin, it is rich in flexibility and excellent in aroma retention. From this, it was confirmed that the laminated sheet for medical patch of the present invention can be preferably used in the form of, for example, a plaster sheet or a poultice sheet. Ninth Example Next, an anti-fog film made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single site catalyst will be described.

This anti-fog film is prepared by adding one or more surfactants to a polyolefin having a syndiotactic structure, particularly polypropylene, obtained by a polymerization reaction using a single-site catalyst to form a film. It is molded.

Here, as the surfactant, various conventionally known surfactants are used, and nonionic surfactants are particularly preferably used. As the nonionic surfactant, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, glycerin fatty acid ester, oxyethylene-
Examples thereof include oxypropylene block copolymer, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol sugar and the like. Here, as the acid group of the fatty acid ester, lauric acid, palmitic acid, stearic acid, and oleic acid are generally used. The number of moles of ethylene oxide added to the polyoxyethylene alkyl ether is not particularly limited, but is usually 4 to 10 moles.

100% by weight of polyolefin having a syndiotactic structure polymerized by using the single site catalyst
The addition rate of the above-mentioned surfactant with respect to
It is 5% by weight, preferably 0.1 to 3% by weight. If the addition rate of this surfactant is less than 0.05% by weight, the desired antifogging property may not be obtained in some cases. On the other hand, if the addition rate of the surfactant exceeds 5% by weight, the bleed-out of the surfactant on the surface becomes excessive, which may cause stickiness or affect the heat sealability, and the antifogging effect. The sex may decrease.

In the present invention, in addition to the above-mentioned surfactant, if necessary, an inorganic or organic filler, an antioxidant, an ultraviolet absorber, an antistatic agent, an antiblocking agent, a lubricant, and a flame retardant agent. Agents, dyes, pigments and the like may be added appropriately.

For example, silicon dioxide, zeolite, aluminosilicate, fine powder talc, etc., having an average particle size of 0.3 to
Addition of an inorganic substance having a thickness of about 15 μm can provide lubricity and improve antifogging property.

The method of adding the surfactant and other additives is not particularly limited, but, for example, the resin and the surfactant are melt-blended in advance with a Banbury mixer or a kneader to form a master batch, which is mixed in a predetermined manner. Examples include a method of adjusting the ratio and a method of directly mixing the resin pellets.

The method for forming the film is not particularly limited, but examples thereof include a T-die method and an inflation method. The thickness of the antifogging film is not particularly limited, but is usually about 5 to 100 μm.

In the present invention, the antifogging film obtained as described above may be laminated with the base film. Here, as the substrate film, stretched polypropylene, unstretched polypropylene, stretched polyethylene terephthalate,
Unstretched polyethylene terephthalate, stretched polyamide,
Examples include unstretched polyamide, polycarbonate, cellophane, polyacetate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer and the like. These substrate films may be a film coated with nitrification cotton, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride or the like on the surface thereof, or silicon oxide on the surface of the substrate film, It may be a film obtained by vapor deposition of an inorganic substance such as aluminum oxide. Moreover, one or more kinds of these base material films may be stuck together. The thickness of the base film is usually about 9 to 100 μm. Printing may be performed on the base film.

The method for laminating the anti-fog film and the base film is not particularly limited, and examples thereof include an extrusion sand lamination method and a dry lamination method.
In the extrusion sand lamination method, for example, as shown in FIG.
As shown in, the anchor coating agent 20 is applied to the base film 10 on which the printing 10a is applied, and the high-pressure low-density polyethylene 30 is used to carry out sand lamination with the anti-fog film 5. In this case, if ozone-containing gas is blown onto the surface of the extruded low density polyethylene molten film, the adhesiveness is improved.

In the present invention, the antifogging film described above may be extrusion-laminated on the base film, or the antifogging film and the base film may be coextruded.

The use of this anti-fog film is not particularly limited, but it is preferably used as a packaging material for foods containing water, for example. Hereinafter, the antifogging film of the present invention will be described more specifically based on Experimental Examples. Experimental Example 13 A polypropylene having a syndiotactic structure (a density of 0.88) obtained by a polymerization reaction using a single-site catalyst
g / cm ³ , melt index [MI]: 3),
Add 0.6 wt% sorbitan monostearate,
A single layer antifogging film having a thickness of 30 μm was obtained by the T-die method.

Next, the thickness 12 applied with vinylidene chloride
An isocyanate-based anchor coating agent was applied to a biaxially stretched polyethylene terephthalate having a thickness of 15 μm, and a high-pressure low-density polyethylene having a thickness of 15 μm (a density of 0.923 g / cm ³ ,
The above single-layer antifogging film was subjected to sand lamination through [MI]: 7) to obtain a multilayer antifogging film.

With respect to the multilayer antifogging film thus obtained, the antifogging property and the low temperature sealing property were evaluated.
The results are shown in Table 1. The antifogging property was evaluated at 35 ° C.
The opening of a 200 ml beaker containing 100 ml of water was covered with a multilayer anti-fog film so that the anti-fog surface faces the inside of the beaker, and after cooling at 5 ° C for 10 minutes, the anti-fog surface (sample The state of dew condensation on the surface) was examined and evaluated according to the following three grades.

◯: The entire surface is uniformly wet. Δ: Large water drops are attached. X: Fine water drops adhered and there was a cloudy portion.

The evaluation of the low temperature sealing property was carried out as follows. That is, using a heat seal tester (manufactured by Tester Sangyo Co., Ltd.), the anti-fog surfaces are sealed at a pressure of 2 kg / cm.
_2. Heat sealing was performed at each temperature under the condition that the sealing time was 1 second. Then, it was cut into a width of 15 mm and the seal strength was measured. The rising temperature of the sealing strength was obtained from the sealing strength at each temperature, and the rising temperature of the sealing strength was evaluated as the heat sealing start temperature.

[0091]

[Table 9] Comparative Example 16 In Experimental Example 13, polypropylene having a syndiotactic structure (density 0.88 g / cm ³ , melt index [MI]: 3) obtained by a polymerization reaction using a single-site catalyst was added to 0.6% by weight. Sorbitan monostearate was added, and an ethylene-1-hexene copolymer polymerized using a Ziegler-based catalyst was used in place of the single-layer anti-fog film having a thickness of 30 μm formed by the T-die method, and an inflation method was used. Thickness of 30μm
A multilayer anti-fog film was prepared in the same manner as in Example 1 except that the above anti-fog film was used, and the obtained multilayer anti-fog film was evaluated for anti-fog property and low-temperature sealing property. The results are shown in Table 9. Examination of Results As is clear from Table 9, the antifogging film of Experimental Example 13 using polypropylene with a syndiotactic structure polymerized using a single-site catalyst was an isotactic polymer polymerized using a conventional Ziegler-based catalyst. It can be seen that the anti-fogging property and the low-temperature sealing property are excellent as compared with the anti-fogging film of Comparative Example 16 using the polypropylene having the structure.

[0092]

As described in detail above, the package of the present invention comprises a polyolefin film composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst, either alone or laminated with another layer. Therefore, according to the present invention, since it is formed into a desired shape,
The following effects are achieved. (1) If a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded into a food packaging pouch in which the innermost layer is the polyolefin layer, aroma retaining property is obtained. A pouch for food packaging, which has excellent heat-sealing properties, sealing strength, transparency, and physical properties and does not cause so-called citrus skin can be obtained. (2) When a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded into a tube container, it is excellent in transparency, surface gloss, cold shock resistance and squeeze resistance. Can be a tube container. (3) When a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded into a paper container whose innermost layer is the polyolefin layer, the odor is transferred to the contents. It is possible to obtain a paper container having no aroma and excellent in aroma retention. (4) A single blank plate made of a laminated material having a polyolefin layer made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst and having only a body is placed in a molding die, By injecting the syndiotactic structure polyolefin obtained by the polymerization reaction using a single-site catalyst to this, the joint gaps, bottoms and openings at both ends of the blank plate are filled with the syndiotactic structure polyolefin to form the innermost layer. When molded into a composite container which is a syndiotactic polyolefin, it is possible to obtain a high-strength composite container which has no odor transfer to the contents and is excellent in aroma retention. (5) If a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded alone into a medical packaging material, it is excellent in transparency, flexibility and physical properties, such as Ringer's solution and glucose solution. The medical packaging material can be used as a medical bag or the like that can be suitably used for storing a liquid drug or containing a waste liquid during artificial dialysis. (6) When a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is molded into a medical packaging material in which the innermost layer is a polyolefin layer, there is little radiation deterioration. The medical packaging material can be suitably used as a container for medical use. (7) By forming a syndiotactic structure polyolefin obtained by a polymerization reaction using a single-site catalyst into a laminated sheet for medical patches, a laminated sheet for medical patches excellent in flexibility and aroma retention is obtained. can do. (8) When a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst is used to form an anti-fog film, it has excellent anti-fog properties, low temperature sealability, hot tack property, seal strength, etc. An anti-fog film having a good filling machine suitability can be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a package of the present invention.

FIG. 2 is an explanatory view showing an example of the package of the present invention.

FIG. 3 is an explanatory view showing an example of a package of the present invention.

FIG. 4 is an explanatory view showing an example of a package of the present invention.

FIG. 5 is an explanatory view showing an example of the package of the present invention.

FIG. 6 is an explanatory view showing an example of the package of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Tube container 2 ... Gobel top type paper container 3 ... Paper cup 4 ... Composite container 5 ... Anti-fog film

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Masanori Takahashi 1-1-1 Ichigayakamachi, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd.

Claims (19)

[Claims] 1. A package comprising a polyolefin film made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst, alone or laminated with another layer to give a desired shape. 2. The package according to claim 1, wherein the polyolefin is polypropylene. 3. A package formed by molding a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into a pouch for food packaging, the innermost layer of which is the polyolefin layer. . 4. The package according to claim 3, wherein the polyolefin is polypropylene. 5. A package formed by molding a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single site catalyst into a tube container. 6. The package according to claim 5, wherein the polyolefin is polypropylene. 7. A package formed by molding a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into a paper container whose innermost layer is the polyolefin layer. 8. The package according to claim 7, wherein the polyolefin is polypropylene. 9. A single blank plate made of a laminated material having a polyolefin layer made of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst and having only a body portion is placed in a molding die. The innermost layer is filled with the polyolefin, and the innermost layer is filled with the polyolefin to have a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst. A package formed integrally with a composite container that is a polyolefin layer. 10. The package according to claim 9, wherein the polyolefin is polypropylene. 11. A package formed by molding a polyolefin having a syndiotactic structure, which is obtained by a polymerization reaction using a single-site catalyst, alone into a medical packaging material. 12. A package formed by molding a laminated material having a polyolefin layer composed of a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into a medical packaging material in which the innermost layer is the polyolefin layer. 13. A package formed by molding a polyolefin sheet having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into a laminated sheet for medical patch. 14. A package formed by molding an anti-fog film composition obtained by adding one or more surfactants to a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst into an anti-fog film. . 15. The package according to claim 14, wherein the addition rate of the surfactant is 0.05 to 5% by weight with respect to 100% by weight of the polyolefin. 16. A package formed by laminating the anti-fogging film according to claim 14 on a base film. 17. An antifog film formed by extruding a base film layer and an antifog film layer obtained by adding one or more surfactants to a polyolefin having a syndiotactic structure obtained by a polymerization reaction using a single-site catalyst to form an antifog film. A package formed by forming a film. 18. The package according to claim 17, wherein the addition rate of the surfactant is 0.05 to 5% by weight with respect to 100% by weight of the polyolefin. 19. The package according to claim 14 or 17, wherein the polyolefin is polypropylene.