WO2010016404A1 - 多層液体容器 - Google Patents
多層液体容器 Download PDFInfo
- Publication number
- WO2010016404A1 WO2010016404A1 PCT/JP2009/063333 JP2009063333W WO2010016404A1 WO 2010016404 A1 WO2010016404 A1 WO 2010016404A1 JP 2009063333 W JP2009063333 W JP 2009063333W WO 2010016404 A1 WO2010016404 A1 WO 2010016404A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin
- discharge port
- liquid container
- mainly composed
- multilayer
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/52—Details
- B65D75/58—Opening or contents-removing devices added or incorporated during package manufacture
- B65D75/5861—Spouts
- B65D75/5872—Non-integral spouts
- B65D75/5883—Non-integral spouts connected to the package at the sealed junction of two package walls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/10—Bag-type containers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/14—Details; Accessories therefor
- A61J1/1475—Inlet or outlet ports
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Definitions
- the present invention relates to a resin multilayer liquid container having a discharge port, and more specifically, prevents the active ingredient of the content liquid from adsorbing and permeating not only the container body but also the resin constituting the discharge port.
- the present invention relates to a multilayer liquid container that can be sterilized at a high temperature and has high welding strength and drop strength at the discharge port.
- a soft bag formulation in which a drug for injection is diluted in advance as a formulation for intravenous infusion and filled in a flexible container such as a plastic, and the soft bag formulation is convenient for use.
- a drug for injection is diluted in advance as a formulation for intravenous infusion and filled in a flexible container such as a plastic
- the soft bag formulation is convenient for use.
- it is also useful because it is more disposable than glass bottles and ampoules.
- drugs including protein-containing preparations such as nitroglycerin, albumin, and hormones, hyaluronic acid preparations, vitamins, trace elements, insulin, anticancer agents, radical scavenging preparations, etc. are polyethylene (PE) and It is known to adsorb or permeate the base material of pharmaceutical containers such as ordinary polyolefin resin (PO resin) such as polypropylene (PP) and vinyl chloride, and the active ingredients of the content liquid can be adsorbed to the base material. It has been a problem in developing a soft bag formulation, such as the interaction between the contained additive and low molecular weight components and the content liquid.
- PO resin polypropylene
- Patent Document 1 Japanese Patent Application Laid-Open No. 2004-298220
- COP resin cyclic polyolefin resin
- Patent Document 2 discloses that a COP resin, which has been conventionally used for a prefilled syringe container, is applied to a soft bag.
- the innermost layer is made of polyethylene resin (PE resin) to increase the drop impact strength as a container and maintain sufficient strength as a liquid storage container. A certain effect of reducing the action is observed.
- the innermost layer is a polyethylene resin, the effect of preventing component adsorption and interaction with the content liquid is inferior to that of conventional glass containers, and sufficient problems have not been solved.
- the COP resin has a larger molecular weight and is more linear than low density polyethylene and has a bulky molecular structure with a cyclic hydrocarbon group in the molecular skeleton, so that the thermal motion of the molecular main chain is limited.
- a cyclic hydrocarbon group in the molecular skeleton, so that the thermal motion of the molecular main chain is limited.
- it when formed into a film, it tends to be a hard and brittle film. Therefore, in order to make the base film of a soft bag, it is common to laminate
- Patent Document 3 discloses a packaging bag made of a laminated film having a PO resin as an outer layer and a COP resin as an inner layer, and is capable of high-pressure steam sterilization and adsorbing components. It is described that it is suitable for use in injectable preparations that are easily adsorbed because of their low properties.
- Patent Document 4 describes a soft bag in which a layer made of a COP resin or a resin containing a COP resin and a polyester resin or PO resin are laminated.
- the innermost layer is preferably a COP resin layer from the viewpoint of component adsorptivity.
- these soft bags are usually provided with a discharge port (port) for discharging the chemical solution.
- the discharge port member it is said that it is necessary to use a discharge port member formed of COP resin in the same manner because of the weldability with the COP resin of the innermost layer of the bag.
- the discharge port member is molded with only a very expensive COP resin as compared with the PO resin, the amount of resin used is large and the cost is inferior.
- the COP resin itself is hard and brittle as described above, the welded portion between the COP resins is brittle to impact and bending from the outside even when the weld strength is high, and is easily damaged at the periphery of the discharge port when dropped. There's a problem.
- the cap covering the rubber plug portion is welded in order to prevent the rubber plug portion from falling off, there are similar cap cost and brittleness of the welded portion.
- the cap itself is COP, there is a high risk of breakage as a result of impact concentration on the cap portion when it is dropped. Therefore, there has been a demand for the development of a soft bag that does not adsorb or permeate drugs and that is not damaged even by an impact such as dropping.
- JP-A-2005-254508 JP-A-2005-254508
- Patent Document 3 describes that a COP resin is blended with a thermoplastic elastomer to give flexibility.
- Japanese Patent Application Laid-Open No. 2005-254508 Patent Document 3 may use a two-color molded port using COP resin for the innermost layer and linear low density polyethylene (LLDPE) for the outermost layer.
- LLDPE linear low density polyethylene
- specific resin properties and welding modes are not disclosed at all. In particular, regarding the welding mode between the film and the discharge port, the two-color molding port is not used in the examples, and there is no specific disclosure regarding the welding strength between the film and the discharge port.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2008-18063 also discloses that the innermost layer of the container film is made of COP resin, and the outlet is made of LLDPE, COP resin produced using a single-site catalyst, and multilayers thereof. It is described that a discharged outlet may be used. However, in the weld strength test, only the weld strength between the films on the peripheral edge of the container is disclosed, and there is no disclosure regarding the weld strength between the film and the discharge port.
- JP 2004-298220 A JP 2008-29829 A JP 2005-254508 A JP 2006-081898 A JP 2008-18063 A
- the present invention has been made in view of the above circumstances, and prevents the active ingredient of the content liquid from adsorbing and permeating not only the container main body but also the resin constituting the discharge port, and performing high-temperature sterilization treatment.
- Another object of the present invention is to provide a multi-layer liquid container having a high discharge strength and a drop strength.
- the innermost layer is composed of a resin mainly composed of a cyclic olefin resin
- the main part of the surface layer is composed of a specific polyethylene as a major component.
- Multi-layer liquid containers with a discharge port composed of a resin that is welded under a specific condition to a sealant made of a resin mainly composed of a cyclic olefin-based resin, not only the container body but also the discharge port It has been found that the resin constituting it can be prevented from adsorbing and permeating, and can be sterilized at high temperature, and has a high welding strength and drop strength at the discharge port, and has led to the present invention. .
- Claim 1 A multilayer in which at least one discharge port having a cross-sectional structure perpendicular to the discharge path is welded to a part of a container made of a multilayer film in which a resin sealant mainly composed of a cyclic olefin resin is laminated on one side.
- a liquid container, The innermost layer forming the discharge path of the discharge port is composed of a resin mainly composed of a cyclic olefin resin, and the main part of the surface layer is composed of a resin mainly composed of polyethylene polymerized by a metallocene catalyst.
- a part of the resin whose main component is the cyclic olefin-based resin in the innermost layer of the discharge port is in a strip shape along the edge of the multilayer film on the surface layer of the discharge port
- a resin mainly composed of a cyclic olefin-based resin which has become a subordinate part of the surface layer and a resin mainly composed of polyethylene polymerized by a metallocene catalyst of the main part of the surface layer A multilayer liquid container which is welded to the sealant in a strip shape. Claim 2: 2.
- Claim 3 In the welded portion, the ratio of the weld width of the resin mainly composed of polyethylene polymerized by the metallocene catalyst to the weld width of the resin mainly composed of the cyclic olefin resin is 95: 5 to 5:95.
- Claim 4 The multilayer according to any one of claims 1 to 3, wherein the polyethylene polymerized by the metallocene catalyst is a linear polyethylene and has a density of 880 to 970 kg / m 3.
- Claim 5 The resin mainly composed of polyethylene polymerized by the metallocene catalyst at the outlet is polyethylene alone polymerized by the metallocene catalyst, polyethylene polymerized by the metallocene catalyst, cyclic olefin resin, medium density polyethylene or The multilayer liquid container according to any one of claims 1 to 4, which is a mixture with high-density polyethylene.
- Claim 6 The resin composed mainly of an outlet polyethylene polymerized by a metallocene catalyst is, density 935 ⁇ 970kg / m 3 of high density polyethylene, characterized in that it contains in the range of less than 40 wt% claim 5, wherein Multi-layer liquid container.
- Claim 7 The innermost layer of the outlet has a resin component content with a polystyrene-equivalent number average molecular weight of 3,000 or less by gel permeation chromatography analysis using toluene as a solvent.
- Claim 8 The cyclic olefin resin, which is a resin mainly composed of a cyclic olefin resin, in the innermost layer of the discharge port, is represented by the following general formula (1) and / or (2): The multilayer liquid container according to item.
- Claim 9 In the laminated structure of the discharge port, a concave portion and / or a convex portion are formed on a resin layer side mainly composed of polyethylene polymerized by a metallocene catalyst of a resin layer mainly composed of a cyclic olefin resin. 9. The multilayer liquid container according to any one of 1 to 8.
- Claim 10 The multilayer liquid container according to any one of claims 1 to 9, wherein a cap having a rubber stopper is welded to the discharge port.
- Claim 11 The multilayer liquid container according to any one of claims 1 to 10, wherein the container is capable of high-temperature sterilization at 105 ° C or higher.
- the present invention it is possible to prevent the active ingredient of the content liquid from adsorbing and permeating not only the container body but also the resin constituting the discharge port, and high-temperature sterilization treatment, Since there are two types of welded portions in the welded portion of the discharge port, it is possible to provide a multilayer liquid container having a high weld strength and drop strength of the discharge port.
- FIG. 1 is a plan view of a multilayer liquid container 1 of the present invention.
- 2 and 3 are cross-sectional views of the vicinity of the discharge port of the first embodiment of the multilayer liquid container 1 of the present invention.
- the multilayer liquid container 1 of the present invention is a bag-like container in which the periphery of a film or tube is welded, or a blow-molded container, in which at least one discharge port 2 is welded.
- a film and a sheet are referred to as a film without distinction.
- the “main component” means a component containing 50% by mass or more.
- the multi-layer films 11 and 12 of the multi-layer liquid container 1 are configured such that the sealants 111 and 121 are both composed mainly of COP resin.
- PO resin or the like is usually laminated to ensure flexibility. However, you may laminate
- the multilayer films 11 and 12 may be the same or different.
- the sealants 111 and 121 may be the same or different, but from the viewpoint of weldability, the sealants 111 and 121 are preferably composed of a resin having the same COP resin as a main component.
- lamination can be performed by coextrusion molding such as multilayer inflation molding and multilayer T die casting, extrusion lamination in which molten resin is directly laminated, or dry lamination using an adhesive.
- coextrusion molding such as multilayer inflation molding and multilayer T die casting
- extrusion lamination in which molten resin is directly laminated
- dry lamination using an adhesive.
- adhesive resins represented by Mitsui Chemicals' Admer, Mitsubishi Chemical's Modic, etc. Can also be used.
- Examples of the PO resin include conventionally known high density polyethylene (HDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), polypropylene (PP), and thermoplastic elastomers thereof and blends thereof. It can. When these PO resins are used, it is possible to impart both heat resistance and flexibility to the container.
- HDPE high density polyethylene
- LLDPE linear low density polyethylene
- MDPE medium density polyethylene
- PP polypropylene
- thermoplastic elastomers thereof and blends thereof it can.
- the total thickness of the multilayer films 11 and 12 is not particularly limited, but is generally 70 to 400 ⁇ m.
- the sealants 111 and 121 mainly composed of COP resin are 15 to 150 ⁇ m, more preferably 50 to 100 ⁇ m.
- the thickness of the sealants 111 and 121 is less than 15 ⁇ m, the welding strength with the discharge port 2 may not be sufficient.
- the sealants 111 and 121 are thinned by heating and pressurization, which may cause liquid leakage due to pinholes.
- the thickness of the sealants 111 and 121 may exceed 150 ⁇ m, but if the thickness is increased, the flexibility of the container may be inferior. Further, it is not preferable in terms of cost.
- a base film such as a stretched film or a layer imparting barrier properties may be laminated in order to ensure strength.
- a layer imparting barrier properties such as oxygen barrier properties and water vapor barrier properties, ethylene vinyl alcohol copolymer, polyvinyl alcohol or coating film thereof, MXD nylon, polyvinylidene chloride or coating film thereof, fluorine-based film, alumina-deposited polyester, Resin layers such as nylon, silica-deposited polyester and nylon can be used.
- the multilayer films 11 and 12 form a multilayer liquid container 1 by welding a necessary portion by a known means to form a peripheral portion or by welding to the discharge port 2. As a method of welding, heat sealing is generally used, but ultrasonic sealing or high frequency sealing may be used.
- the multilayer films 11 and 12 may have bulges formed by vacuum forming or pressure forming.
- multilayer extrusion blow molding is suitably employed.
- a multilayer coextrusion blow molding method a multi-layer extruder having a plurality of extruders is used to melt COP resin and PO resin, and if necessary, adhesive resin and other synthetic resins in each extruder. Extrude and blow mold by blowing air.
- the preform may be once blow molded after being formed into a preform, or each molten resin layer may be formed into a tubular multilayer parison inside the multilayer parison molding die, and direct blow molding may be performed. Good.
- At least one discharge port 2 is provided in a part of the multilayer liquid container 1.
- the discharge port 2 can also be used as a filling port.
- the discharge port 2 is welded by stacking the sealants 111 and 121 of the multilayer films 11 and 12 and inserting the discharge port 2 between them to weld by heat sealing. To do.
- the multilayer liquid container 1 is blow-molded, the multilayer liquid container 1 is welded at the time of molding by insert molding in which the discharge port 2 is inserted into the mold during molding.
- the multilayer container which has an opening part is shape
- the innermost layer 21 that comes into contact with the discharge path as a discharge path is made of a resin mainly composed of a COP resin in order to prevent the adsorption and permeation of the active components of the inner solution.
- the resin will be described later.
- the discharge port welded with the multilayer films 11 and 12 of the multilayer liquid container 1 The surface layer 22 of 2 is mostly composed of a resin mainly composed of polyethylene polymerized by a metallocene catalyst having a density of 880 to 970 kg / m 3 .
- a part is made of a resin mainly composed of COP resin. That is, the main part of the surface layer is composed of a resin mainly composed of polyethylene polymerized by a metallocene catalyst, and the outlet 2 is welded to the sealants 111 and 121 of the multilayer films 11 and 12, A part of the resin mainly composed of COP resin is exposed on the surface of the discharge port 2 in a strip shape along the edges of the multilayer films 11 and 12.
- the band-shaped portion of the resin mainly composed of the COP resin may be extended to the storage portion side (downward in the drawing) of the multilayer liquid container.
- “main part” means a part that occupies 50% or more of the surface area of the surface layer of the discharge port
- dependent part means the surface layer of the discharge port. It means a portion occupying less than 50% of the surface area.
- the portion where the resin containing the COP resin as the main component (the portion having the width III) is exposed on the surface layer 22 of the discharge port 2 is the resin layer of the welded portion 3. Since it becomes a COP resin, the welding strength is high. On the other hand, details will be described later, but this portion is fragile. On the other hand, if there is a belt-like part (resin having a width II) of a resin mainly composed of PE polymerized by a metallocene-based catalyst, an impact when the welded part 3 is dropped is welded by the resin layer (having a width II). Part) is absorbed or dispersed.
- the strength (drop strength) against an impact at the time of dropping is improved. That is, according to the present invention, since there are two kinds of welded portions in the welded portion 3, the weld strength is high, and the welded portion 3 of the discharge port 2 can be prevented from being damaged, and there is no fear of liquid leakage.
- the layer made of a resin mainly composed of PE polymerized by the metallocene catalyst is a layer made of a different resin for welding the sealants 111 and 121 used for the multilayer films 11 and 12 with the COP resin. Regardless, it is possible to perform welding with high strength. And the welding intensity
- the surface layer 22 of the outlet 2 is mainly composed of PE resin polymerized by a metallocene catalyst. is important.
- the PE resin polymerized by a catalyst other than the metallocene catalyst has a wide molecular weight distribution, and a large amount of low softening point components and low molecular weight components are present. When welding with the COP resin, these bleed out to the weld surface and affect the weldability, which causes a decrease in weldability.
- the low softening point component existing at the weld interface of the PE resin and the low molecular weight component that bleeds out to the surface of the PE resin and affects the weldability are extremely reduced.
- the PE resin is a linear low-density polyethylene, the ⁇ -olefin side chain is appropriately introduced, so that the ⁇ -olefin side chain easily enters between the molecules. It becomes possible to obtain welding strength.
- the conditions when such molecular chain entanglement occurs are a density of 880 to 970 kg / m 3 , preferably 900 to 960 kg / m 3 , more preferably 935 to 955 kg / m 3 .
- the density is 935 to 955 kg / m 3
- the welding strength with the resin containing COP resin as a main component is increased, the heat resistance is further improved, and the temperature of the high temperature sterilization treatment can be 115 ° C. or higher. More preferred.
- the density is less than 880 kg / m 3 , the heat resistance may not be sufficient, and problems such as deformation of the discharge port may occur during high temperature sterilization.
- the density exceeds 970 kg / m 3 the welding strength with a resin containing COP resin as a main component is lowered, so that it can be used but the practical welding strength may not be obtained.
- the resin component content of the polystyrene-equivalent number average molecular weight of 3,000 or less by gel permeation chromatography analysis using toluene as a solvent is 1% by mass or less. It is preferable because there is no elution of low molecular components or adsorption of active components of chemical solutions.
- the number average molecular weight in terms of polystyrene by gel permeation chromatography analysis using toluene as a solvent is 10,000 to 200,000, preferably 20,000 to 100,000, more preferably 25,000 to 50,000. 000 is preferable because it is excellent in mechanical strength and heat resistance.
- the resin mainly composed of polyethylene polymerized with a metallocene catalyst has high heat resistance when blended with HDPE or the above-mentioned COP resin in a range of 40% by mass or less, preferably 30% by mass or less. Since it improves, it is preferable. However, the heat resistance improves as the blending amount of HDPE or COP resin increases. On the other hand, if the blending ratio of HDPE exceeds 40% by mass, the welding strength with the multilayer film may not be sufficient, and the blending ratio of COP resin. If it exceeds 40% by mass, the welded portion 3 may become brittle and drop strength may be reduced.
- a resin mainly composed of polyethylene polymerized by a metallocene-based catalyst contains linear polyethylene as a main component if these are contained in an amount of 40% by mass or less, more preferably 30% by mass or less. Even in the case of the above resin, the temperature of the high temperature sterilization treatment can be set to 121 ° C. or higher.
- HDPE to be contained in a resin mainly composed of polyethylene polymerized by a metallocene catalyst can impart appropriate hardness and high heat resistance to the outlet 2 when the density is 935 to 970 kg / m 3. It is preferable because it is possible.
- the sealant 111, 121 of the multilayer films 11, 12, and the COP resin of the discharge port 2 and the portion that becomes the main component of the COP resin are exposed in the welded portion 3 in a band shape, so that the sealant
- the welding strength with 111 and 121 is also high and stable.
- the COP resin that is the main component of the sealants 111 and 121 is preferably the same or very similar to the COP resin that is the main component of the innermost layer 21 of the discharge port 2, but the film grade and the molding grade And so on.
- both the sealants 111 and 121 of the multilayer films 11 and 12 and the surface layer 22 of the discharge port 2 are made of COP resin, a welding strength of 30 N / 15 mm or more can be obtained, but a container that can withstand high-temperature sterilization suitable for the present invention.
- the COP resin as a sealant used in the above is generally as small as 3 to 60% in elongation at break and hard at a flexural modulus of 2,000 to 3,200 MPa, and therefore has a very brittle property due to external impact.
- the container sealant is composed of a flexible material having a bending elastic modulus of 100 to 700 MPa, which is sufficiently stretched to 700 to 1,000% at break elongation like PE resin used in ordinary containers,
- the welded portion 3 of the discharge port 2 is easily broken, and there is a risk of liquid leakage.
- Such a situation is hardly said to be welded with practical welding strength.
- the discharge port 2 has a part of the resin mainly composed of COP resin welded to the multilayer films 11 and 12 exposed on the surface layer of the discharge port 2 in a strip shape along the edge of the multilayer films 11 and 12. ing. Then, at least a part of the resin whose main component is the exposed outermost layer (surface) COP resin and the resin whose main component is PE polymerized by the metallocene catalyst are both welded to the sealant.
- the outlet 2 is arranged so that the resin mainly composed of PE polymerized by the metallocene catalyst does not exist at the end of the outlet 2 on the welded part 3 side. Is formed.
- the inner solution and the discharge port 2 are connected to the metallocene in the flow path from the inner solution storage portion of the multilayer liquid container 1 to the discharge port 2. It does not come into contact with a resin mainly composed of PE polymerized by the system catalyst. That is, since the contact surface of the inner solution is composed only of the COP resin, the content component is adsorbed by the multilayer films 11 and 12 and the discharge port 2 or permeated through the multilayer films 11 and 12 and the discharge port 2. There is no. Therefore, it is preferable because the content content of the inner solution is not lowered or the content liquid is not deteriorated or contaminated by the interaction with the multilayer films 11 and 12 and the discharge port 2.
- the range of the exposed width is not particularly limited as long as the resin mainly composed of the COP resin is exposed in the welded portion 3, but the width where the resin mainly composed of the COP resin is exposed.
- the range of (Width III) is 1 to 20 mm, preferably 2 to 15 mm, more preferably 3 to 10 mm.
- the range of the exposed width may be less than 1 mm, but if it is too narrow, it may hinder the formation of the discharge port 2. Moreover, although it may exceed 20 mm, the improvement of welding strength cannot be expected and it may be unpreferable in terms of cost.
- the ratio of the welding width (width II) of the resin mainly composed of PE polymerized by the metallocene catalyst to the welding width (width III) of the resin mainly containing the COP resin is 95: 5.
- a resin mainly composed of the COP resin of the sealants 111 and 121 and the COP resin of the discharge port 2 High weld strength due to the welded portion, and brittleness relaxation due to the welded portion between the COP resin in the innermost layer of the multilayer films 11 and 12 and the resin mainly composed of PE polymerized by the metallocene catalyst in the outlet 2
- the balance with is preferable.
- the brittleness of the welded portion 3 is improved while ensuring a high weld strength of the welded portion 3 with the multilayer liquid container 1 outlet 2. That is, the multilayer liquid container 1 having excellent drop strength can be obtained by reflecting the welding strength of 30 N / 15 mm or more by the resin mainly composed of COP resin.
- the present embodiment there is no resin whose main component is PE polymerized by a metallocene catalyst on the lower end surface layer of the discharge port 2 on the side of the storage portion of the multilayer liquid container 1, and the COP resin is the main component. Only resin. Thereby, since the active ingredient of the content liquid is not adsorbed to the multi-layer liquid container 1 or permeate the multi-layer liquid container 1, the content of the component is reduced, the interaction with the multi-layer liquid container 1, etc. As a result, the content liquid is not deteriorated or contaminated.
- FIG. 4 is a cross-sectional view of the vicinity of the discharge port of the second embodiment of the multilayer liquid container 1 of the present invention.
- the present embodiment is different from the first embodiment only in that the unevenness 6 shown in FIG. 4 is provided.
- the resin mainly composed of PE polymerized by the metallocene catalyst used in the main part of the surface layer 22 is HDPE, MDPE or LDPE alone or when the mixing ratio is high, The welding strength between the innermost layer 21 at the outlet 2 and the resin layer mainly composed of PE polymerized by the metallocene catalyst may not be sufficient.
- the recesses and projections are preferably irregularities 6 including a plurality of annular recesses and projections, but may be a single annular recess or projection. Or this unevenness
- corrugation 6 may not be cyclic
- it may be provided anywhere.
- FIG. 5 is a cross-sectional view of the vicinity of the discharge port of the third embodiment of the multilayer liquid container 1 of the present invention.
- This embodiment is different from the first and second embodiments in that the multilayer liquid container 1 according to this embodiment has a welded portion formed by a resin layer mainly composed of COP resin in an intermediate portion of the welded portion of the discharge port 2. It is only a point that exists.
- the lower end surface layer on the storage unit side of the multilayer liquid container 1 is also a resin whose main component is PE polymerized by a metallocene catalyst.
- the resin layer mainly composed of PE polymerized by the metallocene catalyst at the lower end of the discharge port 2 may come into contact with the inner solution, but the multilayer films 11 and 12 of the multilayer liquid container 1 are welded. 3 is in close contact with the lower end of the discharge port 2, so that the influence of the resin mainly composed of PE polymerized by the metallocene catalyst is small.
- the multi-layer liquid container filled with the inner solution has a long storage period, it is preferably applied to an inner solution that does not contain a component that is greatly affected by adsorption or permeation.
- Examples of the COP resin used for the sealants 111 and 121 and the discharge port 2 of the multilayer films 11 and 12 in the present invention include, for example, polymers of various cyclic olefin monomers and co-polymerization of cyclic olefin monomers with other monomers such as ethylene. And coalesced and hydrogenated products thereof.
- the COP resin used for the multilayer films 11 and 12 and the discharge port 2 is preferably substantially the same resin even if there is a difference in the difference between the film grade and the molding grade. It may be.
- Examples of the cyclic olefin monomer that is polymerized as a COP resin used for the sealants 111 and 121 of the multilayer films 11 and 12 and the outlet 2 include, for example, norbornene, norbornadiene, methylnorbornene, dimethylnorbornene, ethylnorbornene, chlorinated norbornene, chloromethylnorbornene, Bicyclic cycloolefins such as trimethylsilylnorbornene, phenylnorbornene, cyanonorbornene, dicyanonorbornene, methoxycarbonylnorbornene, pyridylnorbornene, nadic anhydride, nadic imide; dicyclopentadiene, dihydrodicyclopentadiene and its alkyl, alkenyl, alkylidene, Tricyclic cycloolefins such as aryl substituents; dimethan
- dinorbornene a compound in which two norbornene rings are bonded by a hydrocarbon chain or an ester group, and a compound containing a norbornene ring such as an alkyl or aryl substituent thereof can be used.
- polynorbornene resins obtained by polymerizing one or more of norbornene monomers having a norbornene skeleton in the molecular skeleton such as dicyclopentadiene, norbornene, and tetracyclododecene, or hydrogenated products thereof , And a mixture of two or more thereof are suitable as the sealants 111 and 121 of the multilayer films 11 and 12 and the innermost layer 21 of the discharge port 2 in the present invention.
- the polymerization method and polymerization mechanism of the monomer molecules of the COP resin in the present invention may be ring-opening polymerization or addition polymerization.
- addition polymerization those polymerized using a metallocene catalyst are preferred.
- a known polymer can be used by using a known method. Alternatively, it may be blended after polymerization to some extent to form a block copolymer.
- the COP resins listed above as the COP resins used for the sealants 111 and 121 and the discharge port 2 in the present invention those represented by the structural formula represented by the following general formula (1) or (2) are preferable.
- the COP resin represented by the following general formula (1) is particularly preferable because it is particularly excellent in film-forming suitability and can be manufactured at a lower cost when the discharge port 2 is formed.
- the COP resin represented by the general formula (2) cannot form the sealants 111 and 121 of the multilayer films 11 and 12 or the innermost layer 21 of the discharge port 2 with the COP resin alone. It is necessary to blend and use PE resin for the purpose of improving suitability.
- R 1 , R 2 , R 3 and R 4 are the same or different organic groups having 1 to 20 carbon atoms, and R 1 and R 2 and / or R 3 and R 4 are (The ring may form a ring.
- M and p represent 0 or an integer of 1 or more.
- L and n represent an integer of 1 or more.
- examples of the organic group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, i-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, t-octyl (1,1-dimethyl-3,3-dimethylbutyl), 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Alkyl groups such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl,
- the glass transition temperature of such a COP resin can be appropriately adjusted by appropriately selecting the values of l, m, n, and p in the above general formulas (1) and (2), or substituents. .
- the glass transition temperature of the COP resin other than the above general formulas (1) and (2) is also arbitrarily adjusted by appropriately setting the monomer type to be used, the blending ratio of the monomer type, the monomer sequence, the type of substituent, and the like. be able to.
- COP resin represented by the general formula (1) Commercially available products can be used as the COP resin represented by the general formula (1), and for example, ZEONEX and ZEONOR manufactured by ZEON Corporation can be suitably used.
- commercially available products can be used as the COP resin represented by the general formula (2), and for example, Appell manufactured by Mitsui Chemicals, Inc. and TOPAS manufactured by TICONA Inc. can be preferably used.
- the COP resin used for the sealants 111 and 121 and the discharge port 2 of the multilayer films 11 and 12 in the present invention it is preferable to use the one represented by the general formula (1), and the COP represented by the general formula (1). More preferably, it is composed of a resin alone and does not contain other resins.
- the COP resin represented by the general formula (2) it is possible to use a blend of PE resin or the like at a ratio of about 10 to 40% by mass in order to prevent gel generated during film formation. preferable.
- the content of ethylene is small and the content of the cyclic olefin is large because of excellent heat resistance.
- the discharge port 2 is formed by multicolor molding or insert molding of two or more colors. A conventionally known method can be adopted as the molding method.
- the tip of the discharge port 2 is opened at the time of soft bag manufacture.
- a cap having a hole around the rubber plug 4 is inserted after a filling nozzle is inserted through the opening 23 to fill the content liquid and replace with nitrogen.
- 5 is fitted with a rubber plug fitted in advance, and welded and sealed with an ultrasonic sealer or the like.
- the resin layer mainly composed of PE polymerized by the metallocene catalyst is extended and exposed to the tip of the outlet 2
- the cap 5 is composed of PE polymerized by the metallocene catalyst as a main component.
- the rubber plug 4 is a rubber plug that is normally used, a conventionally known one can be used as it is.
- examples of such rubber plugs include butyl rubber, isoprene rubber, chlorinated butyl rubber, and silicon rubber as they are, or laminated rubber plugs that are coated with fluorine resin, ultra high molecular weight polyethylene, high molecular weight polyethylene, LLDPE, or the like.
- the rubber stopper 4 may be made using an elastomer resin. In this case, the molding process of the rubber plug 4 is shortened, and the adsorption of the content liquid is small.
- the multilayer liquid container 1 of the present invention is mainly used for storing medical liquids, deformation or deformation of the multilayer liquid container 1 can be achieved by high-temperature sterilization treatment at 105 ° C. or higher, preferably 115 ° C. or higher, more preferably 121 ° C. or higher. It is necessary to have a configuration without bag breaking. Therefore, the COP resin used for the sealants 111 and 121 of the multilayer films 11 and 12 and the discharge port 2 in the present invention preferably has a glass transition temperature of 100 ° C. or higher, preferably 110 ° C. or higher.
- Example 1 Creation of multilayer films 11 and 12: COP resin ZEONOR 70 manufactured by Nippon Zeon Co., Ltd. having an outermost layer 112,122: 160 ⁇ m made of PP-based elastomer manufactured by Mitsubishi Chemical Co., Ltd. % (Mass ratio) and glass transition temperature 136 ° C.
- outlet 2 60% (mass ratio) of COP resin ZEONOR manufactured by ZEON Corporation having a glass transition temperature of 102 ° C. and 40% (mass ratio) of COP resin ZEONEX manufactured by ZEON Corporation having a glass transition temperature of 136 ° C.
- the resin of the inner layer 21 was used.
- the resin of the main part of the innermost layer 21 and the surface layer 22 is laminated and molded by a two-color molding method, and the resin of the innermost layer is exposed on the surface layer on the end side of the discharge port 2 in a portion corresponding to the welded part 3.
- the discharge port has a substantially cylindrical shape with a total length of 40 mm and a diameter of 17 mm at a portion corresponding to the welded portion. Creation of multilayer liquid container 1: A peripheral portion was welded with one discharge port 2 sandwiched between the multilayer films 11 and 12, and the multilayer liquid container 1 having a width of 115 mm and a length of 170 mm shown in FIG.
- the welding width was 5 mm on both side edges and 3 mm at the narrowest side, and the welding conditions were welding at 260 ° C. for 4 seconds at and around the discharge port 2. On the opposite side of the discharge port 2, a hole 7 for hanging on the hook was provided.
- Structure of welded part 3 The welded portion 3 of the multilayer films 11 and 12 and the discharge port 2 has the form shown in FIG. 2 and is welded with a resin whose main component is PE polymerized by a metallocene catalyst with an overall width I of 10 mm.
- the multilayer liquid container 1 is filled with 100 ml of purified water from the outlet 2 and subjected to high-temperature sterilization treatment at 115 ° C. for 40 minutes, and then stored in a 4 ° C. environment for 24 hours. Then, the test was carried out by letting it fall naturally on the concrete.
- the drop test was carried out with the discharge port 2 facing downward so that it always fell from the discharge port 2 to the concrete, and the same multilayer liquid container 1 was repeatedly dropped five times to perform the test. As a result, it was found that there was no bag breakage and no liquid leakage, and it had a sufficient drop strength.
- Example 2 Creation of multilayer films 11 and 12: Same as Example 1.
- Creation of outlet 2 It was the same as Example 1 except having set it as the discharge port 2 shown in FIG.
- Creation of multilayer liquid container 1 Same as Example 1.
- Structure of welded part 3 The overall width I of the welded portion 3 is 10 mm, the weld width II with a resin mainly composed of PE polymerized by a metallocene catalyst is 6 mm, and the COP resin that is the innermost layer and is exposed on the outermost layer is the main component.
- Measurement of welding strength The welding strength of the welded part 3 was measured in the same manner as in Example 1.
- Example 3 Creation of multilayer films 11 and 12: Same as Example 1.
- Creation of outlet 2 A cylindrical product made of COP resin having a thickness of 1 mm and indicated by reference numeral 21 in FIG. 2 was injection molded in advance using the same COP resin as in Example 1.
- To the metallocene LLDPE having a density of 930 kg / m 3 (manufactured by Tosoh Corporation), HDPE having a density of 963 kg / m 3 (manufactured by Tosoh Corporation) is blended so that the ratio of LLDPE: HDPE is 80:20 (mass ratio),
- the cylindrical object was placed in a mold, and the cylindrical object made of COP resin was covered by an insert molding method, and the discharge port 2 shown in FIG.
- Example 4 Creation of multilayer films 11 and 12: Same as Example 1.
- Creation of outlet 2 A discharge port 2 was created in the same manner as in Example 1 except that the ring-shaped drop-off preventing unevenness 6 shown in FIG. 4 was provided on the surface layer 22 side of the resin layer containing the COP resin as the main component of the innermost layer 21.
- Creation of multilayer liquid container 1 Same as Example 1.
- Structure of welded part 3 Same as Example 1.
- Measurement of welding strength The welding strength of the welded part 3 was measured in the same manner as in Example 1. The result was 35 N / 15 mm and had a very high welding strength.
- Example 5 Creation of multilayer films 11 and 12: Same as Example 1.
- Creation of outlet 2 Except for using the metallocene-based LLDPE (manufactured by Ube Maruzen Polyethylene Co., Ltd.) with a density of 935 kg / m 3 used in Example 1 as the resin of the main part of the surface layer 22, it was molded by insert molding as in Example 3, The discharge port 2 shown in FIG. 2 was created.
- Creation of multilayer container 1 Same as Example 1.
- Structure of welded part 3 Same as Example 1.
- Measurement of welding strength The welding strength of the welded part 3 was measured in the same manner as in Example 1. The result was 44 N / 15 mm and had a very high welding strength.
- Example 7 Creation of multilayer films 11 and 12: Same as Example 6. Creation of outlet 2: Same as Example 1. Creation of multilayer liquid container 1: Same as Example 1. Structure of welded part 3: Same as Example 1. Measurement of welding strength: The welding strength of the welded part 3 was measured in the same manner as in Example 1. The result was 42 N / 15 mm and had a very high welding strength. On the other hand, when the welded portions at the side edges of the multilayer films 11 and 12 were also measured in the same manner as in Example 1, the weld strength was 33 N / 15 mm. Drop impact test: The test was performed in the same manner as in Example 1. As a result, it was found that there was no bag breakage and no liquid leakage, and it had sufficient strength.
- Measurement of welding strength The welding strength of the welded part 3 was measured in the same manner as in Example 1. The result was 45 N / 15 mm and had a very high welding strength. On the other hand, when the welded portions at the side edges of the multilayer films 11 and 12 were also measured in the same manner as in Example 1, the weld strength was 30 N / 15 mm.
- Drop impact test The test was performed in the same manner as in Example 1. As a result, it was found that there was no bag breakage and no liquid leakage, and it had a sufficient drop strength.
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Abstract
Description
この容器は、最内層をポリエチレン系樹脂(PE樹脂)で構成することにより、容器としての落下衝撃強度を強くし、液体保存容器として十分な強度を保ちながら、同時に成分吸着や内容液との相互作用を低減化する一定の効果が認められる。しかし、最内層がポリエチレン系樹脂であるために、従来のガラス製容器に比べて成分吸着や内容液との相互作用を防止する効果は劣り、充分な問題解決には至っていない。
請求項1:
環状オレフィン系樹脂を主成分とする樹脂のシーラントが一面に積層された多層フィルムからなる容器の一部に、排出路に直交する断面が積層構造を有する排出口が少なくとも1つ以上溶着された多層液体容器であって、
前記排出口の排出路を形成する最内層が環状オレフィン系樹脂を主成分とする樹脂で構成され、かつ表層の主要部がメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂で構成されるとともに、
前記排出口が前記シーラントと溶着される溶着部において、 前記排出口の最内層の環状オレフィン系樹脂を主成分とする樹脂の一部が前記排出口の表層に前記多層フィルムの端縁に沿う帯状に露出して、表層の従属部となった環状オレフィン系樹脂を主成分とする樹脂の少なくとも一部と表層の主要部のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂との双方が前記シーラントと帯状に溶着されてなることを特徴とする多層液体容器。
請求項2:
前記排出口の前記溶着部側の端部の表層に、メタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が存在しないことを特徴とする請求項1記載の多層液体容器。
請求項3:
前記溶着部において、メタロセン系触媒により重合されたポリエチレンを主成分とする樹脂による溶着幅と環状オレフィン系樹脂を主成分とする樹脂とによる溶着幅の比率が、95:5~5:95である請求項1又は2記載の多層液体容器。
請求項4:
前記メタロセン系触媒により重合されたポリエチレンが、直鎖状のポリエチレンであって、その密度が880~970kg/m3であることを特徴とする請求項1~3のいずれか1項に記載の多層液体容器。
請求項5:
前記排出口のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が、メタロセン系触媒により重合されたポリエチレン単独、又はメタロセン系触媒により重合されたポリエチレンと、環状オレフィン系樹脂、中密度ポリエチレンもしくは高密度ポリエチレンとの混合物であることを特徴とする請求項1~4のいずれか1項に記載の多層液体容器。
請求項6:
前記排出口のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が、密度935~970kg/m3の高密度ポリエチレンを40質量%以下の範囲で含有することを特徴とする請求項5記載の多層液体容器。
請求項7:
前記排出口の最内層の、環状オレフィン系樹脂を主成分とする樹脂が、トルエンを溶媒としたゲル・パーミエーション・クロマトグラフィー分析によるポリスチレン換算の数平均分子量3,000以下の樹脂成分含有量が1質量%以下であることを特徴とする請求項1~6のいずれか1項に記載の多層液体容器。
請求項8:
前記排出口の最内層の、環状オレフィン系樹脂を主成分とする樹脂の環状オレフィン系樹脂が、次の一般式(1)及び/又は(2)で示される請求項1~7のいずれか1項に記載の多層液体容器。
請求項9:
前記排出口の積層構造において、環状オレフィン系樹脂を主成分とする樹脂層のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂層側に凹部及び/又は凸部が形成されている請求項1~8のいずれか1項に記載の多層液体容器。
請求項10:
前記排出口にゴム栓を備えるキャップが溶着された請求項1~9のいずれか1項に記載の多層液体容器。
請求項11:
前記容器が105℃以上の高温滅菌処理が可能である請求項1~10のいずれか1項に記載の多層液体容器。
図1は、本発明の多層液体容器1の平面図である。
図2及び3は、本発明の多層液体容器1の第1の形態例の排出口近傍の断面図である。
本発明の多層液体容器1は、排出口2が少なくとも1つ以上溶着された、フィルムやチューブの周辺を溶着した袋状容器、あるいはブロー成形した容器である。
なお、本明細書においては、フィルムもシートも区別することなくフィルムと呼ぶものとにする。また、「主成分」とは、50質量%以上含む成分を意味する。
また、COP樹脂とPO樹脂等とを共押出成形で積層する場合は、これらを直接積層してもよいが、三井化学社製のアドマー、三菱化学社製のモディックなどに代表される接着性樹脂を用いることもできる。
その場合、COP樹脂を主成分とするシーラント111,121は、15~150μm、より好ましくは50~100μmである。シーラント111,121の厚みが15μm未満では、排出口2との溶着強度が十分でないことがある。また、排出口2を溶着する時にシーラント111,121が加熱・加圧により薄くなり、ピンホールによる液漏れの原因となることがある。シーラント111,121の厚みは150μmを超えてもよいが、厚くなると容器の柔軟性に劣ることがある。また、コスト的にも好ましくない。
酸素バリア性や水蒸気バリア性などのバリア性を付与する層として、エチレンビニルアルコール共重合体、ポリビニルアルコール又はそのコーティングフィルム、MXDナイロン、ポリ塩化ビニリデン又はそのコーティングフィルム、フッ素系フィルム、アルミナ蒸着ポリエステルやナイロン、シリカ蒸着ポリエステルやナイロンなどの樹脂層を使用することができる。
溶着する方法は、ヒートシールが一般的であるが、超音波シールや高周波シールを用いてもよい。多層フィルム11,12は、真空成形や圧空成形で膨らみが形成されていてもよい。
排出口2の溶着方法は、多層液体容器1が袋状容器である場合は、多層フィルム11,12のシーラント111,121同士を重ね合わせて、その間に排出口2を挿入してヒートシールで溶着する。
また、多層液体容器1がブロー成形の場合には、成形時に排出口2を金型内に挿入するインサート成形により、多層液体容器1の成形時に溶着する。あるいは開口部を有する多層容器を成形し、あとから開口部に排出口2を挿入してヒートシールで溶着する。
そして、COP樹脂を主成分とする樹脂の使用量を抑えるため、及び、排出口2の溶着部3の脆性を改良するために、多層液体容器1の多層フィルム11,12と溶着される排出口2の表層22は、密度880~970kg/m3であるメタロセン系触媒によって重合されたポリエチレンを主成分とする樹脂で大部分が構成される。一方、溶着部3の溶着性を確保するために、一部は、COP樹脂を主成分とする樹脂で構成される。
即ち、表層の主要部がメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂で構成されるとともに、排出口2が多層フィルム11,12のシーラント111,121と溶着される溶着部3において、COP樹脂を主成分とする樹脂の一部が排出口2の表面に多層フィルム11,12の端縁に沿う帯状に露出する。そして、露出して表層の従属部となったCOP樹脂を主成分とする樹脂の少なくとも一部とメタロセン系触媒によって重合されたPEを主成分とする樹脂との双方が前記シーラント11,12と帯状に溶着される。従って、図2及び3においては、COP樹脂を主成分とする樹脂の帯状の部分は、多層液体容器の収納部側(図の下方)に延設されていてもよい。
なお、本明細書においては、排出口の表層について、「主要部」とは、排出口の表層の表面積の50%以上を占める部分を意味し、「従属部」とは、排出口の表層の表面積の50%未満を占める部分を意味する。
一方、メタロセン系触媒によって重合されたPEを主成分とする樹脂の帯状の部分(幅IIを有する部分)が存在すると溶着部3の落下時の衝撃を該樹脂層による溶着部(幅IIを有する部分)が吸収又は分散する。これにより落下時の衝撃に対する強度(落下強度)が向上する。
即ち、本発明は、溶着部3に2種類の溶着部が存在するので、溶着強度が高く、かつ排出口2の溶着部3の破損を防止することが可能となり、液漏れの心配がなくなる。
メタロセン系触媒以外の触媒により重合されたPE樹脂は、分子量分布も広く、低軟化点の成分や低分子量成分が多量に存在する。COP樹脂と溶着を行なうに際し、これらが溶着面にブリードアウトして溶着性に影響するので、溶着性が低下する原因となる。一方、メタロセン系触媒によりPE樹脂を重合すると、該PE樹脂の溶着界面に存在する低軟化点成分や該PE樹脂の表面にブリードアウトして溶着性に影響する低分子量成分が極めて少なくなる。その結果として、直鎖状で、分子骨格に環状炭化水素基による嵩高い分子構造を有するCOP樹脂の分子鎖と該PE樹脂の分子鎖のからみ合いを構築し易くなる。
この時、該PE樹脂が直鎖状低密度ポリエチレンであると、適度にα-オレフィンの側鎖が導入されているため、分子間にα-オレフィンの側鎖が入り込み易くなるので、より強固な溶着強度を得ることが可能になる。
また、メタロセン系触媒により重合されたポリエチレンを主成分とする樹脂に含有させるHDPEは、密度が935~970kg/m3であると、排出口2に適度な硬さと高い耐熱性を付与することが出来るので好ましい。
本形態例においては、図2及び3に示すように、排出口2の溶着部3側の端部にメタロセン系触媒によって重合されたPEを主成分とする樹脂が存在しない様に、排出口2が形成される。この様に形成された排出口2が多層フィルム11,12に溶着されると、多層液体容器1の内溶液収納部から排出口2の流路内において、内溶液と排出口2とが、メタロセン系触媒によって重合されたPEを主成分とする樹脂と接することがない。つまり、内溶液の接触面がCOP樹脂のみで構成されるので、内容成分が、多層フィルム11,12や排出口2に吸着されたり、多層フィルム11,12や排出口2を透過したりすることがない。したがって、内溶液の成分含有量が低下したり、多層フィルム11,12や排出口2との相互作用等により内容液が劣化や汚染されることがないので好ましい。
本発明においては、例えば、表層22の主部に使用されるメタロセン系触媒によって重合されたPEを主成分とする樹脂がHDPE、MDPEやLDPE単独の場合又はその混合割合が高い場合には、排出口2の最内層21とメタロセン系触媒によって重合されたPEを主成分とする樹脂層との溶着強度が十分ではなくなることがある。
この様な場合は、最内層21のメタロセン系触媒によって重合されたPEを主成分とする樹脂層側に凹及び/又は凸部を形成することが好ましい。この凹部や凸部は、図4に示すように、複数の環状の凹部と凸部からなる凹凸6であることが好ましいが、一本の環状の凹部や凸部であってもよい。あるいは、この凹凸6は、環状でなくてもよいし、連続しない単なる凹部と凸部がランダムに設けられていてもよい。また、最内層21のメタロセン系触媒によって重合されたPEを主成分とする樹脂層側であれば、どこに設けても良い。この凹凸6により、排出口2の最内層21とメタロセン系触媒によって重合されたPEを主成分とする樹脂層との接着強度が十分ではない場合であっても、最内層21とメタロセン系触媒によって重合されたPEを主成分とする樹脂層とが剥離して脱落することを防止できる。
本形態例は、多層液体容器1の収納部側の下端表層もメタロセン系触媒によって重合されたPEを主成分とする樹脂とする態様である。この場合は、排出口2の下端部のメタロセン系触媒によって重合されたPEを主成分とする樹脂層が内溶液に接する可能性があるが、多層液体容器1の多層フィルム11,12が溶着部3で排出口2の下端に密着しているので、実質的にメタロセン系触媒によって重合されたPEを主成分とする樹脂の影響は小さい。しかし、内溶液が充填された多層液体容器の保存期間が長い場合も考慮すると、吸着や透過による影響が大きい成分を含有しない内溶液に対して適用することが好ましい。この様にCOP樹脂を主成分とする樹脂層がメタロセン系触媒によって重合されたPEを主成分とする樹脂層からなる表層間に表出すると、COP樹脂を主成分とする樹脂層による溶着部の脆さがメタロセン系触媒によって重合されたPEを主成分とする樹脂層により効果的にカバーされる。したがって、落下強度が大幅に向上し、スルーホールの発生を有効に防止することが出来る。
これらのうち、ジシクロペンタジエン、ノルボルネン、テトラシクロドデセンといった、分子骨格中にノルボルネン骨格を含むノルボルネン系モノマーの1種又は2種以上を重合して得られるポリノルボルネン系樹脂、又はその水素添加物、及びそれらを1種又は2種以上を混合したものが、本発明における多層フィルム11,12のシーラント111,121及び排出口2の最内層21として好適である。
上記一般式(2)で示されるCOP樹脂の場合には、フィルムの製膜時に発生するゲルを防止するために、PE樹脂等を10~40質量%程度の割合でブレンドして使用することが好ましい。上記一般式(2)で示されるCOP樹脂の場合には、エチレンの含有量が少なく、環状オレフィンの含有量が多いと耐熱性に優れるので好ましい。
多層フィルム11,12の作成:
三菱化学社製のPP系エラストマーからなる最外層112,122:160μm、三菱化学社製のモディックからなる図示しない接着性樹脂層:30μm、ガラス転移温度102℃の日本ゼオン社製のCOP樹脂ゼオノア70%(質量比)とガラス転移温度136℃の日本ゼオン社製のCOP樹脂ゼオネックス30%(質量比)のブレンドからなるシーラント111,121:60μmを積層した総厚み:250μmの樹脂層を水冷多層インフレーション法により製膜し、図2に示す多層フィルム11,12とした。
排出口2の作成:
ガラス転移温度102℃の日本ゼオン社製のCOP樹脂ゼオノア60%(質量比)とガラス転移温度136℃の日本ゼオン社製のCOP樹脂ゼオネックス40%(質量比)をブレンドし、排出口2の最内層21の樹脂とした。密度935kg/m3のメタロセン系LLDPE(宇部丸善ポリエチレン社製)を単独で使用し、排出口2の表層22の主要部の樹脂とした。最内層21及び表層22の主要部の樹脂を二色成形法で積層成形し、溶着部3に相当する部分に排出口2の端部側の表層に最内層の樹脂が露出している図2に示す排出口2を作成した。排出口は、全長40mm、溶着部に相当する個所で直径が17mmの略円筒状とした
多層液体容器1の作成:
多層フィルム11,12間に排出口2を1個挟んで周縁部を溶着し、図1に示す幅115mm、長さ170mmの多層液体容器1を作成した。溶着幅は、両側縁で5mm、最も狭いところで、3mmとし、溶着の条件は、排出口2の周辺及びそれ以外とも、260℃で4秒間溶着を行なった。排出口2の反対側には、フックに吊るすための孔7を設けた。
溶着部3の構成:
多層フィルム11,12と排出口2の溶着部3は、図2に示す態様とし、溶着部3の全体の幅Iを10mm、メタロセン系触媒によって重合されたPEを主成分とする樹脂との溶着幅IIを9mm、COP樹脂を主成分とする樹脂との溶着幅IIIを1mmとした(II:III=90:10)。
溶着強度の測定:
多層フィルム11,12と排出口2の溶着部3の溶着強度の測定に際しては、排出口2と多層フィルム11,12とを多層液体容器1から切り出した。多層フィルム11,12の排出口2の中央付近で流路に沿う方向に5mm間隔の切れ目を2本入れて、多層フィルム11,12の5mm幅の自由端を作成した。多層フィルム11,12のそれぞれの5mm幅の自由端を測定機のチャックに固定してフィルム11,12を引っ張り、JIS-Z0238に準拠して測定した。測定値は、15mm幅に換算した。
結果は、45N/15mmであり、極めて高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても同様に測定した。但し、側縁の溶着部は、溶着部に直交する方向に15mm幅で切り出して測定した。結果は、溶着強度は30N/15mmであった。
落下衝撃試験:
多層液体容器1に排出口2から100mlの精製水を充填し、115℃にて高温滅菌処理を40分間実施した後、4℃環境下で24時間保管して、その状態で1.5mの高さからコンクリート上に自然落下させて試験を行なった。落下試験は排出口2を下にして常に排出口2からコンクリートに落ちるように実施し、同一の多層液体容器1を繰り返し5回落下させて試験を実施した。結果は、破袋、液漏れはなく、十分な落下強度を有していることが判った。
多層フィルム11,12の作成:
実施例1と同様とした。
排出口2の作成:
図3に示す排出口2としたこと以外は、実施例1と同様とした。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
溶着部3の全体の幅Iを10mm、メタロセン系触媒によって重合されたPEを主成分とする樹脂との溶着幅IIを6mm、最内層であって最外層に表出したCOP樹脂を主成分とする樹脂層21との溶着幅IIIを4mmとした(II:III=60:40)。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、42N/15mmであり、極めて高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は32N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な落下強度を有していることが判った。
多層フィルム11,12の作成:
実施例1と同様とした。
排出口2の作成:
実施例1と同様のCOP樹脂で予め肉厚1mmの図2の符号21に示されるCOP樹脂製の円筒状物を射出成型した。密度930kg/m3のメタロセン系LLDPE(東ソー社製)に、密度963kg/m3のHDPE(東ソー社製)を、LLDPE:HDPEが80:20(質量比)の割合となるように配合し、金型に上記円筒状物を配置すると共に、インサート成形法でCOP樹脂製の円筒状物を被覆し、実施例1と同様な図2に示す排出口2を作成した。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、40N/15mmであり、極めて高い溶着強度を有している。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は30N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な落下強度を有していることが判った。
多層フィルム11,12の作成:
実施例1と同様とした。
排出口2の作成:
図4に示すリング状の脱落防止用凹凸6を最内層21のCOP樹脂を主成分とする樹脂層の表層22側に設けたこと以外は、実施例1と同様に排出口2を作成した。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、35N/15mmであり、極めて高い溶着強度を有していた。
多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は30N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な落下強度を有していることが判った。
多層フィルム11,12の作成:
実施例1と同様とした。
排出口2の作成:
表層22の主要部の樹脂として、実施例1で用いた密度935kg/m3のメタロセン系LLDPE(宇部丸善ポリエチレン社製)を用いたこと以外は、実施例3と同様にインサート成形で成形し、図2に示す排出口2を作成した。
多層容器1の作成:
実施例1と同様とした。
溶着部3の構成:
実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、44N/15mmであり、極めて高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は30N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な強度を有していることが判った。
多層フィルム11,12の作成:
密度936kg/m3のHDPE(東ソー社製)からなる最外層112,122:15μm、
密度925kg/m3のLLDPE(プライムポリマー社製)からなる最外層112,122に隣接する図示しない第1の中間層:150μm、
密度910kg/m3のLLDPE(日本ポリエチレン社製)からなる図示しない第1の中間層とシーラント111,121とに接する図示しない第2の中間層:25μm、
ガラス転移温度102℃の日本ゼオン社製のCOP樹脂ゼオノア60%(質量比)とガラス転移温度136℃の日本ゼオン社製のCOP樹脂ゼオネックス40%(質量比)のブレンドからなるシーラント111,121:60μmとを積層した総厚み250μmの図2に示す多層フィルム11,12を多層Tダイ共押出法により製膜した。
排出口2の作成:
実施例3と同様とした。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、40N/15mmであり、高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は33N/15mmであった。
落下衝撃試験:
滅菌を121℃、30分間とした以外は、実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な強度を有していることが判った。
多層フィルム11,12の作成:
実施例6と同様とした。
排出口2の作成:
実施例1と同様とした。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、42N/15mmであり、極めて高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は33N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な強度を有していることが判った。
多層フィルム11,12の作成:
密度935kg/m3のLLDPE(東ソー社製)からなる最外層112,122:40μm、密度925kg/m3のLLDPE(プライムポリマー社製)と密度905kg/m3のLLDPE(日本ポリエチレン社製)を9:1(質量比)でブレンドしてなる図示しない中間層:150μm、ガラス転移温度102℃の日本ゼオン社製のCOP樹脂ゼオノア60%(質量比)とガラス転移温度136℃の日本ゼオン社製のCOP樹脂ゼオネックス40%(質量比)のブレンドからなるシーラント111,121:60μmとを積層した総厚み250μmの図5に示す多層フィルム11,12を多層共押出Tダイ法により製膜した。
排出口2の作成:
実施例1と同様とした。
多層液体容器1の作成:
実施例1と同様とした。
溶着部3の構成:
多層フィルム11,12と排出口2の溶着部3は、図5に示す態様とした。溶着部3の全体の幅Iを10mm、COP樹脂を主成分とする樹脂との溶着部を溶着部3の中間に設け、その幅IIIを3mmとした。メタロセン系触媒によって重合されたPEを主成分とする樹脂との溶着幅IIは、図5に示すように5mmと2mmの上下に分割し、その合計を7mとした(II:III=70:30)。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、45N/15mmであり、極めて高い溶着強度を有していた。
一方、多層フィルム11,12同士の側縁の溶着部についても実施例1と同様に測定したところ、溶着強度は30N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、破袋、液漏れはなく、十分な落下強度を有していることが判った。
多層フィルムの作成:
実施例1と同様とした。
排出口の作成:
最内層21のCOP樹脂を主成分とする樹脂が表層22に露出することなく積層されたこと以外は、実施例1の排出口と同様とした。
多層容器の作成:
実施例1と同様とした。
溶着部3の構成:
多層フィルムと排出口の溶着部の全てを最外層22のメタロセン系触媒によって重合されたPEを主成分とする樹脂との溶着としたこと以外は、実施例1と同様とした。
溶着強度の測定:
溶着部3の溶着強度を実施例1と同様に測定した。結果は、21N/15mmであり、溶着強度は低かった。
一方、多層フィルム同士の周縁の溶着部についても同様に測定したところ、溶着強度は30N/15mmであった。
落下衝撃試験:
実施例1と同様の方法で試験を行なった。
結果は、落下1回では破袋、液漏れともなかったが、3回目の落下で排出口周縁部からの液漏れが発生した。
11,12 多層フィルム
111,121 多層フィルムのシーラント
2 排出口
21 排出口の最内層
22 排出口の表層
3 溶着部
4 ゴム栓
5 キャップ
6 凹凸
7 孔
Claims (11)
- 環状オレフィン系樹脂を主成分とする樹脂のシーラントが一面に積層された多層フィルムからなる容器の一部に、排出路に直交する断面が積層構造を有する排出口が少なくとも1つ以上溶着された多層液体容器であって、
前記排出口の排出路を形成する最内層が環状オレフィン系樹脂を主成分とする樹脂で構成され、かつ表層の主要部がメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂で構成されるとともに、
前記排出口が前記シーラントと溶着される溶着部において、 前記排出口の最内層の環状オレフィン系樹脂を主成分とする樹脂の一部が前記排出口の表層に前記多層フィルムの端縁に沿う帯状に露出して、表層の従属部となった環状オレフィン系樹脂を主成分とする樹脂の少なくとも一部と表層の主要部のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂との双方が前記シーラントと帯状に溶着されてなることを特徴とする多層液体容器。 - 前記排出口の前記溶着部側の端部の表層に、メタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が存在しないことを特徴とする請求項1記載の多層液体容器。
- 前記溶着部において、メタロセン系触媒により重合されたポリエチレンを主成分とする樹脂による溶着幅と環状オレフィン系樹脂を主成分とする樹脂とによる溶着幅の比率が、95:5~5:95である請求項1又は2記載の多層液体容器。
- 前記メタロセン系触媒により重合されたポリエチレンが、直鎖状のポリエチレンであって、その密度が880~970kg/m3であることを特徴とする請求項1~3のいずれか1項に記載の多層液体容器。
- 前記排出口のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が、メタロセン系触媒により重合されたポリエチレン単独、又はメタロセン系触媒により重合されたポリエチレンと、環状オレフィン系樹脂、中密度ポリエチレンもしくは高密度ポリエチレンとの混合物であることを特徴とする請求項1~4のいずれか1項に記載の多層液体容器。
- 前記排出口のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂が、密度935~970kg/m3の高密度ポリエチレンを40質量%以下の範囲で含有することを特徴とする請求項5記載の多層液体容器。
- 前記排出口の最内層の、環状オレフィン系樹脂を主成分とする樹脂が、トルエンを溶媒としたゲル・パーミエーション・クロマトグラフィー分析によるポリスチレン換算の数平均分子量3,000以下の樹脂成分含有量が1質量%以下であることを特徴とする請求項1~6のいずれか1項に記載の多層液体容器。
- 前記排出口の積層構造において、環状オレフィン系樹脂を主成分とする樹脂層のメタロセン系触媒により重合されたポリエチレンを主成分とする樹脂層側に凹部及び/又は凸部が形成されている請求項1~8のいずれか1項に記載の多層液体容器。
- 前記排出口にゴム栓を備えるキャップが溶着された請求項1~9のいずれか1項に記載の多層液体容器。
- 前記容器が105℃以上の高温滅菌処理が可能である請求項1~10のいずれか1項に記載の多層液体容器。
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US13/057,439 US8309189B2 (en) | 2008-08-05 | 2009-07-27 | Multilayered liquid container |
KR1020117004042A KR101917878B1 (ko) | 2008-08-05 | 2009-07-27 | 다층 액체 용기 |
CN200980135659.5A CN102149607B (zh) | 2008-08-05 | 2009-07-27 | 多层液体容器 |
CA2732865A CA2732865C (en) | 2008-08-05 | 2009-07-27 | Multilayered liquid container |
ES09804888T ES2427620T3 (es) | 2008-08-05 | 2009-07-27 | Recipiente multicapa para líquidos |
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ES2427620T3 (es) | 2013-10-31 |
EP2330048A1 (en) | 2011-06-08 |
JP5262407B2 (ja) | 2013-08-14 |
US20110135223A1 (en) | 2011-06-09 |
EP2330048A4 (en) | 2012-04-04 |
CN102149607B (zh) | 2012-12-26 |
KR101917878B1 (ko) | 2019-01-29 |
JP2010036954A (ja) | 2010-02-18 |
US8309189B2 (en) | 2012-11-13 |
CA2732865A1 (en) | 2010-02-11 |
CA2732865C (en) | 2016-03-29 |
EP2330048B1 (en) | 2013-07-03 |
CN102149607A (zh) | 2011-08-10 |
KR20110044878A (ko) | 2011-05-02 |
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