METHOD OF BLOW MOULDING, FILLING AND CLOSING, AND CONTAINER PRODUCT, ESPECIALLY AMPOULE PRODUCT, PRODUCED THEREBY

Abstract

A blow molding, filling and closing process and container product produced accordingly, in particular an ampoule product.

A blow molding, filling and closing process for producing a filled and closed container product that can be stored as well, in particular in the form of an ampoule product which is formed from a plastic material and has a single-layer container wall or ampoule wall and which, during initial use, permits the withdrawal, in particular for an oral use of the product content, by opening at least one withdrawal opening for withdrawal purposes, is characterized in that plastic materials suitable for the process are selected which are tasteless and/or odorless or essentially tasteless and/or odorless in interaction with the contents of the container before and during use and which retain this tastelessness and/or odorlessness even after prolonged storage.

Claims

1. A blow molding, filling and closing process for producing a filled and closed container product that can be stored as well, in particular in the form of an ampoule product which is formed from a plastic material and has a single-layer container wall or ampoule wall and which, during initial use, permits the withdrawal, in particular for an oral use of the product content, by opening at least one withdrawal opening for withdrawal purposes, characterized in that plastic materials suitable for the process are selected which are tasteless and/or odorless or essentially tasteless and/or odorless in interaction with the contents of the container before and during use and which retain this tastelessness and/or odorlessness even after prolonged storage.

2. The process according to claim 1, characterized in that aromatic polyester polymers and/or polyester copolymers and/or blends of these materials are used as plastic materials for the products to be produced.

3. The process according to claim 1, characterized in that temperatures in the range from 250 C. to 280 C. can be selected as processing temperatures for the aromatic polyester polymers and their intrinsic viscosities during processing can be selected to be 0.6 dl/g to 1.7 dl/g.

4. The process according to claim 1, characterized in that the water content of the plastic granulate in the manufacturing process for specifically selected aromatic polyester polymers and/or copolymers immediately prior to extrusion is selected to be less than 50 ppm, preferably 30 ppm.

5. The process according to claim 1, characterized in that 10% to 80%, preferably 30% to 60% reclaimed material is added to the aromatic polyester polymers used.

6. The process according to claim 1, characterized in that at least partially a polyethylene naphthalate (PEN), polyethylene furanoate (PEF) polyester and/or copolyester produced from terephthalic acid, in particular polybutylene terephthalate (PBT), but preferably polyethylene terephthalate (PET), glycol-modified polyethylene terephthalate (PETG), and in each case any copolymers and/or blends thereof is used as relevant aromatic polyester polymer.

7. A container product, in particular ampoule product, produced by a blow molding, filling and closing process according to claim 1, characterized in that the product material is formed from at least one aromatic polyester polymer and/or polyester copolymer and/or polyester copolymer and/or blends at least partially containing these materials.

8. The product according to claim 7, characterized in that the receiving volume for the product to be received and stored, in particular in the form of a liquid, is less than 50 ml.

9. The product according to claim 7, characterized in that the opening cross-section of the relevant withdrawal opening (16), which is opened upon separation of a head part (12) from the remaining product body (10), is smaller than 25 mm2, preferably smaller than 10 mm2.

10. The product according to claim 7, characterized in that the shape of the withdrawal opening (16) deviates from the circular shape and preferably has an oval or polygonal geometry.

11. The product according to claim 7, characterized in that the product body (10) has a non-circular cross-section, preferably an oval or polygonal, particularly preferably a hexagonal cross-section.

12. The product according to claim 7, characterized in that the withdrawal opening (16) has at least one channel, which permits ventilation during the withdrawal of the product.

13. The product according to claim 12, characterized in that the withdrawal opening (16) has at least one channel (40), which is located in the mold parting surface.

14. The product according to claim 12, characterized in that the withdrawal opening (16) comprises at least one channel (40), preferably having a cross-section corresponding approximately to that of a rounded triangle.

15. The product according to claim 7, characterized in that the average wall thickness in the region of the product body (10) intended to contain the relevant product is 0.2 mm to 0.9 mm, preferably 0.3 mm to 0.7 mm, and that the average wall thickness at and in the region of the point of separation or predetermined breaking point (20) is smaller than 0.5 mm, preferably smaller than 0.3 mm.

16. The product according to claim 7, characterized in that the product wall has a high degree of transparency, which permits the product content to be examined visually.

Description

[0027] Below, the procedure according to the invention is explained in more detail using various ampoule products based on the drawing. In the figures, in general view, not to scale,

[0028] FIG. 1 shows a lateral top view of an ampoule product;

[0029] FIG. 2 shows a lateral view of the ampoule product of FIG. 1, which is rotated by 90 around its longitudinal or vertical axis;

[0030] FIGS. 3a, 3b show an exemplary embodiment of an ampoule product having two discharge openings, one in end view, one in side view;

[0031] FIG. 4 shows a perspective view from above onto a further exemplary embodiment of an ampoule product;

[0032] FIG. 5 shows an enlarged and incomplete longitudinal section of another exemplary embodiment of an ampoule having a Luer-cone syringe inserted into the neck of the ampoule; and

[0033] FIG. 6 shows a correspondingly enlarged section along the line VI-VI of FIG. 5.

[0034] The ampoule product shown in FIGS. 1 and 2 is produced according to the Bottelpack process, in which the ampoule product is vacuum-formed, filled and sealed in a workstation. As a rule, such ampoule products are manufactured in a so-called ampoule block, in which several containers are connected to each other in a row.

[0035] The ampoule shown in the figures has an ampoule or product body 10, in which a delivery medium of the ampoule is stored. In this case, the medium to be dispensed is a low-sodium, still mineral water to be able to detect potential changes in taste as easily as possible. The filling quantity of the medium to be dispensed in the product body 10 is approximately 10 ml. A well-known BFS machine of the type Bottelpack 321 by Rommelag was used to produce this 10 ml ampoule.

[0036] Furthermore, the ampoule has a head part 12, which the user can twist off the ampoule body 10 by means of a twist-cap 14, wherein on the upper side of the ampoule body 10 a withdrawal opening 16 can be opened to form an opening cross-section through which the ampoule contents can be withdrawn. As the figures further show, the otherwise cylindrical ampoule body 10 tapers in the direction of a neck part 18, which in the unopened state of the ampoule establishes a connection of the ampoule body 10 and the head part 12 with the twist-cap 14. In order to facilitate detaching the head part 12 using the twist-cap 14, a point of separation or predetermined breaking point 20 is inserted in the ampoule between the connection neck part 18 and the head part 12. Stiffener webs 22 can be used to stiffen the neck section 18, which stiffener webs are integrally formed during the Bottelpack manufacturing process. This design of an ampoule is sufficiently known, accordingly no further details will be given here.

[0037] The aromatic polyesters listed below were used as plastic materials for the manufacture of the ampoule product of FIGS. 1 and 2, wherein any details of the manufacturer and/or trade name are given in brackets: [0038] polyethylene terephthalate (Traytuf 9506, M&G Gruppo Mossi & Ghisolfi), [0039] polyethylene terephthalate copolyester (Polyclear EBM PET 5505, Invista), [0040] polyethylene naphthalate-polyethylene terephthalate-Blend (Hipertuf 85032, Shell Chemicals), [0041] polyethylene furanoate (PEF, Avantium), [0042] copolyesters produced using terephthalic acid (Tritan copolyester MX810, Eastman), [0043] polybutylene terephthalate (Pocan 1501, Lanxess), [0044] polyethylene terephthalate glycol (Eastman MB002 and SK Chemicals S2008).

[0045] Using the aromatic polyester materials mentioned above, ampoules were obtained having glass-like transparency and a surface sheen, which can be inspected using automatic inspection equipment or by the human eye, far better than ampoules having the same geometry and wall thickness, which are made of the known materials polypropylene or low-density polyethylene (LDPE). An automatic inspection system is described for instance in DE 10 2014 006 835 A1 of the patentee.

[0046] The ampoule shown in FIGS. 1 and 2 is also suitable as a container for products that cannot be administered orally, enterally or nasally, such as eye drops, injection or inhalation solutions, suspensions and the like, for which regular inspection of the filled and sealed containers is important and sometimes even required by law.

[0047] Despite the improved mechanical properties (ISO 527-1-2) of the BFS polyester according to the invention having typically high tensile strengths of more than 80 MPa and high tensile coefficient of elasticity of more than 2000 MPa compared to the standard BFS polyolefins (LDPE, HDPE, PP), the ampoules according to the invention can be opened quite easily. Their opening torques are on average 40 Ncm to 55 Ncm, measured using a Vortex-i torque gauge by Mecmesin at a rotational speed of 20 rpm. Such torques can be easily applied by adolescents and adults, i.e. the invented ampoules are particularly suitable for single doses of oral, enteral, sublingual or topical preparations to be used for instance in the oral cavity, such as medications, medicinal products, food supplements, tonics, vitamins, homeopathic remedies, etc.

[0048] The rapid withdrawal of the product by squeezing it out, for instance to apply a solution or emulsion to the tongue, is considerably facilitated if the container can be vented via an additional opening. According to the invention, this can be achieved by opening at least two openings when the ampoule is opened.

[0049] FIGS. 3a and 3b show an exemplary embodiment of an ampoule having two withdrawal openings 16, 17, wherein the larger withdrawal opening 16, for instance, has a diameter of 2 mm, whereas the smaller opening 17 has a diameter of approx. 1 mm. The two withdrawal openings 16, 17 are opened simultaneously, provided that the head part 12 is twisted off the neck part 18 in the known manner by means of the twist-cap 14 via the assigned point of separation or predetermined breaking point from the other ampoule body or product body 10. This ampoule solution can also be provided with pairs of reinforcing webs 22. Except for the two withdrawal openings 16, 17 mentioned, the container according to FIGS. 3a and 3b largely resembles the solution according to FIGS. 1 and 2. The simultaneous opening of the ampoule body 10 via the predetermined breaking point, which can also be designed as a common predetermined breaking point 20, results in a faster emptying of the ampoule product due to the resulting improved ventilation because two withdrawal openings 16, 17 have been opened.

[0050] The metered withdrawal of the product, for instance squeezing out individual drops, is considerably facilitated if the ampoule body 10 does not have a largely circular cross-section, but preferably an oval, diamond-shaped or hexagonal cross-section. The ampoule body 10 of FIG. 4 has such a hexagonal cross-section 10. Also, in this ampoule version the head part 12 can be removed from the neck part 18 of the ampoule body 10 along the point of separation or predetermined breaking point 20 by means of the twist-cap 14, in this case having the form of two handles 24, 26. A syringe needle (not shown) can be inserted into and attached to the ampoule body 10 in a known manner, the end of which needle is then exposed for an application process after the head part 12 has been removed.

[0051] The withdrawal of the product, e.g. sucking it with the aid of a straw inserted through the withdrawal opening 16, is considerably facilitated if the container is vented during withdrawal. According to the invention this can be achieved by designing the withdrawal opening 16 in such a way that an opening cross-section results, which is not circularfor instance ovaland therefore cannot form a seal with the outer surface of the drinking straw.

[0052] The almost complete withdrawal of the product by means of the cone connection of a syringe, for instance for oral (non-Luer-6% connectors, oral tip, EN ISO 80369-3:2016) or dental (6% Luer cone in accordance with EN 1707:1996 and EN 20594-1:1993) applications, is also facilitated if the withdrawal opening 16 permits the container to be vented during withdrawal. According to the invention, this can be achieved by having the geometry of the withdrawal opening 16 deviate only slightly from that of the cone connection to be used. This can be achieved, for instance, by means of at least one longitudinal channel for ventilation, which, however, is just sufficiently small/deep to prevent liquid from escaping during overhead withdrawal. Preferably, at least one ventilation duct is located in the mold parting surface of the container and has a preferred duct cross-section corresponding to that of a rounded triangle.

[0053] Such an aeration chamber solution is shown in FIGS. 5 and 6. The end of the ampoule body 10 opposite the bottom adjoins a first section 28 of the neck part 18, the diameter of which is smaller than the preferably cylindrical diameter of the ampoule body 10 itself due to the conical taper of the ampoule body 10 at its top. This section 28 is followed by a smaller diameter cylindrical section 30, the inner diameter of which is slightly smaller than the largest diameter of the Luer cone 32 of a syringe 34, but slightly larger than the smallest diameter thereof. In this way, a closed, linear contact is achieved between the inserted Luer cone 32 and the inner wall of the neck part 18 in the area of section 30, namely along a cross-sectional plane, as it is shown in FIG. 6 by way of example, which prevents the passage of liquids, but permits the passage of air. In the present embodiment of an ampoule body 10, a protruding thickened rim-like section 36 adjoins section 30 of the neck section 18, the axial length of which rim-like section is selected such that the Luer cone 32 rests against the inner wall of the cylindrical section 30 of the neck section 18 at the required but relatively small contact pressure, which is necessary to prevent the passage of liquids when the end face of the syringe body 34 supporting the Luer cone 32 rests against the free end face 38 of the neck section 18. The syringe 34 docked to the ampoule body 10 preferably has a 9% Luer cone 32 as syringe end. Especially the ampoule product 10 according to FIGS. 1 and 2 as well as FIGS. 3a and 3b can be used similar to extracting the product contents using a suitable Luer cone syringe 34.

[0054] To improve the passage of air between the Luer cone 32 and the neck part 18 in the area of the further section 30, this section 30 is provided with a ventilation channel 40 in the form of an inwardly open longitudinal groove arranged at two points diametrically to the longitudinal axis of the ampoule product 10, the cross-section of which groove is preferably selected in the form of a rounded triangle (see FIG. 6) such that the air flowing in prevents liquid from escaping. Only one single ventilation duct 40 is required to achieve the desired ventilation; if necessary, the cross-section of the duct 40 can be increased accordingly. In case of one ventilation duct 40 only, the outer circumference of the Luer cone 32 rests off-center against the other wall parts of section 30 of the neck section 18. Furthermore, for manufacturing reasons, the ventilation channel 40, which extends in parallel to the longitudinal axis of the ampoule, is advantageously placed in the plane of the mold halves which, when brought together in this plane, permit the ampoule to be shaped.

[0055] In a further, unspecified embodiment of an ampoule made of plastic having a container part for receiving a predeterminable fluid, which container part is provided with a neck part, which can be closed off by a head part, and which has a channel-like entry point for air into the interior of the container part, it may also be provided for effective ventilation that said entry point for air consists of at least one annular channel, which is arranged at least partially on the outside and/or inside circumferential side of the neck part, which enables the container contents to be withdrawn more quickly by means of the syringe or cannula body.

[0056] If the ampoules are to be resealable, that can be achieved by introducing appropriate additional components before the ampoules are sealed. This is described in detail in DE 10 2007 007 474 B3 (Hansen) using a 2-part dropper insert by way of example.

[0057] The intrinsic viscosity of the aromatic polyester polymers used, measured based on ASTM D4603, is preferably in the range from 0.6 dl/g to 1.7 dl/g, and particularly preferably from 0.8 dl/g to 1.5 dl/g.

[0058] In the case of polyethylene terephthalate, polyethylene terephthalate-glycol and their blends and copolymers, an intrinsic viscosity of more than 0.8 dl/g is preferred.

[0059] Furthermore, it has been shown to be advantageous not to select a water content of more than 50 ppm for the granulate immediately prior to extrusion, in particular in the case of polyethylene terephthalate or polyethylene furanoate, and preferably to select a water content of less than 30 ppm.

[0060] The average wall thickness of the ampoule body 10 in the area of the point of separation or predetermined breaking point 20 shall be smaller than 0.45 mm, preferably smaller than 0.3 mm. The average wall thickness of the ampoule in the area of the ampoule body 10 shall be 0.2 mm to 0.9 mm, but preferably 0.3 mm to 0.7 mm. The ampoule shall have a small opening cross-section of less than 25 mm.sup.2, preferably less than 10 mm.sup.2.

[0061] If the criteria of the invention described above are met, a minimization of the organoleptic impairment is achieved for aqueous products, which is surprising because the melting and extrusion temperatures of the aromatic polyester polymers to be used according to the invention at 250 C. to 280 C. are significantly higher than the polyolefins usually used for the BFS manufacturing process, whose processing temperature is typically in the range from 160 C. to 210 C.

[0062] Another advantage of the ampoules according to the invention is the option of using recycled plastic material. 10 to 80%, preferably 30 to 60%, reclaimed material can be added to the original aromatic polyester polymer during manufacture.

[0063] To test the organoleptic properties, a sensory test was performed based on the standard DIN 10955:2004-06. The purpose of the test is to determine whether the BFS polymer used results in an altered smell or taste of the test substance in the form of still, low-sodium mineral water as part of the BFS manufacturing process described above. The test detects odor and aroma transfer, under defined conditions, from the test material either into the air space (odor test) or into the test substance (taste test). This analysis has shown that in using aromatic polyester materials as part of the BFS method only slight taste changes of the test water can be detected by the trained taste testers and that the ampoules made of aromatic polyester polymers were clearly superior to those made of known BFS polyolefins.

[0064] The use of polymers containing polyethylene furanoate is clearly advantageous over the use of the known polyethylene-based plastics. For instance, hot filling, which is preferred for microbiological reasons, or heat treatment of the sealed container to stabilize highly concentrated solutions that tend to crystallize are feasible options.

[0065] Exemplary embodiments of applications are listed below:

[0066] A Bottelpack 321 BFS machine by Rommelag, Waiblingen, Germany, was used. This machine was used to produce ampoules as shown in FIGS. 1, 3 and 4 having a container volume of approximately 10 ml; the ampoules were filled with 5-10 ml of still water low in minerals and taste. The still water was delivered in glass bottles. A PET by M&G Chemicals (Gruppo Mossi & Ghisolfi); type designation Traytuf 9506 was used as polymer materialcf. test number 1. Using a molecular sieve dryer by Digicolor, the granulate was dried to a water content of 36 ppm (mean value from 3 samples) for 10 hours at 120 C. and an air dew point of below minus 30 C. and conveyed to the extruder of the BFS line all the while being protected from moisture. The intrinsic viscosity of the dried polymer was measured based on ASTM D4603 and was found to be 0.94 dl/g. The extrusion temperature during ampoule manufacture was 252 C.; the melt pressure was 262 bar.

[0067] Similarly (cf. test numbers 2 et seqq.), ampoules of different geometries and filling quantities were manufactured from other polymers on different BFS lines. As a reference to the state of the art (cf. test numbers Ref a-c), polystyrene (PS) and, by way of example, the two BFS polyolefins, polypropylene (Purell RP 270G by LyondellBasell) and low-density polyethylene, LDPE (Purell 3020D by LyondellBasell), were used.

[0068] The details of all tests are summarized in the table below.

TABLE-US-00001 Melt volume Mass Mass Ampoule Fill Residual Intrinsic rate pres- temper- Organ- Test According volume moisture viscosity cm.sup.3/ sure ature oleptic No. to Fig. ml polymer type manufacturer desiccation ppm dl/g 10 min bar C. change 1 1 10 PET Traytuf M&G 10 h at 38 0.94 n. a. 262 252 Very low 9506 Chemicals 120 C. 2 1 8 PEF PEF Avantium 18 h at 34 0.88 n. a. 258 256 Very low 150 C. 3 3 8 PBT Pocan Lanxess 6 h at 95 n. a. 16* 251 252 low B1501 125 C. 4 3 5 PETG MB002 Eastman 12 h at 190 0.85 n. a. 237 220 Very low 60 C. 5 4 10 PETG S2008 SK 6 h at 300 1.2 n. a. 222 195 Very low Chemicals 55 C. 6 4 5 PET-Co- MX810 Eastman 6 h at 200 1.1 n. a. 260 205 low polyester 87 C. 7 1 8 PET-Co- Poly- Invista 10 h at 50 1.01 n. a. 285 251 Very low polyester clear 120 C. 5505 Melt flow rate g/10 min Ref-a 1 10 LDPE Purell Lyondell- none n. a. n. a. 0.3** 205 179 high 3020D basell Ref-b 3 10 PP RP270G Lyondell- none n. a. n. a. 1.8*** 200 186 Very high basell Melt volume rate cm.sup.3/ 10 min Ref-c 4 10 PS PS 486N Styrolution none n. a. n. a. 4**** 91 189 Very high *250 C/2.16 kg **190 C/2.16 kg ***230 C/2.16 kg ****200 C/5 kg

[0069] An odor and aroma transfer test was performed based on the standard DIN 10955:2004-06. The purpose of the test was to determine whether the BFS polymer/process used resulted in a change in smell or taste of the test substance (low-sodium, still mineral water). The test detects odor and aroma transfer of agents, which under defined conditions, pass from the test material either into the air space (odor test) or via the air space or in case of direct contact pass into the test substance (taste test). The results, the organoleptic change with respect to the original water, are listed in the table above.

[0070] Surprisingly, the trained taste testers detected only slight taste changes of the test water for the aromatic polyester materials, and ampoules made of the materials PEF, PET and the co-polyester were clearly superior to those of the reference materials (PS, PP and LDPE).