DE202018002336U1 - Apparatus for coating and coated containers - Google Patents

Abstract

Apparatus for carrying out a plasma coating of a plastic container, the apparatus comprising: a station frame (1) with holding rods (2), a plasma chamber (3), a carriage (3) for holding a chamber wall (5), an element for applying a negative pressure to the Container (6), an element for introducing a process gas into the container, a holding element (7) for fixing the container to be treated (6), a microwave generator (8), and an adapter (9) via a coupling channel (10) is connected to the plasma chamber (3), wherein the plasma chamber (3) has a chamber lid (11) which comprises a flange (12) with a seal (13) which seals the chamber wall (5) relative to the chamber lid (11). allows.

Description

The present invention relates to a device for coating a container and the coated container itself.

Coated glass containers for storing liquids are known in the art. So revealed the DE 10 2012 110 131 A1 including glass containers coated with a composite material composed of a substrate and a ceramic protective layer. The aim of the document is to prevent glass delamination during storage and thereby ensure the quality of the liquid contained.

Plastic containers have a number of advantages over glass containers. They are cheaper to manufacture, offer a greater variety of shapes, as well as more flexible, extensive decoration options. Furthermore, plastic containers in mobile use when traveling etc. are advantageous. However, in some cases, plastic containers affect the quality of the liquids filled therein, since diffusion of gases such as carbon dioxide through the wall is more pronounced in plastic bottles than in glass bottles.

Plastic bottles can be coated to protect the liquids from diffusion-related quality losses. Such plastic containers with protective coatings are known in the art. That's how it describes US 4,552,791 a container carrying on its outside a barrier layer of inorganic oxides. Although a reduction of the diffusion is achieved by the coating, these containers have the disadvantage that at low layer thicknesses, the diffusion barrier effect is only insufficient. For larger layer thicknesses, there is a risk of the layer peeling off.

The DE 44 38 359 C2 describes plastic containers with a coating, this coating being composed of at least two barrier layers.

These prior art containers are advantageous in application when diffusion of gases such as oxygen, water vapor, carbon dioxide or flavoring agents through the plastic is to be prevented, but may adversely affect the quality of the contents. Plastic bottles made of polyethylene terephthalate (PET) often cause a fruity-sweet taste impairment in mineral waters. The production and storage of PET bottles can produce acetaldehyde. If this gets into the drink, it can be perceived and smelled even in very small quantities. In drinks with an intense taste, such as juice spritzer, lemonade or cola, the taste impairment is not sensory.

The object of the present invention is therefore to provide a device and a container which overcome the disadvantages of the prior art.

This object is achieved with the features of the independent claims. Advantageous embodiments and developments, which can be used individually or in combination with each other, are the subject of the dependent claims.

The present invention achieves the stated object by providing a device for carrying out a plasma coating of a container, comprising a station frame with holding rods, a plasma chamber, a carriage for holding a chamber wall, an element for applying a negative pressure to the container , an element for introducing a process gas into the container, a holding element for fixing the container to be treated, a microwave generator, and an adapter connected to the plasma chamber via a coupling channel, the plasma chamber having a chamber lid having a flange with a seal comprising, which allows a sealing of the chamber wall relative to the chamber lid. In addition, the device may additionally comprise format parts and / or screw-in devices. The plasma coating may be a Chemical Vapor Deposition (CVD) coating or a Plasma Impulse Chemical Vapor Deposition (PICVD) coating.

It is advantageous if the element for applying a negative pressure to the container and / or the element for introducing a process gas into the container is a gas lance.

The present object is further achieved in that the invention provides a coated plastic container obtainable by the following method: introducing a container into a plasma chamber, sealing the chamber wall by a flange on a chamber lid, applying a negative pressure to a container, inserting the process gas into the container, igniting a plasma by means of radiated electromagnetic energy in the process gas introduced, wherein the coating contains at least one silicon compound and argon and oxygen, the argon in an amount of 10 to 60%, preferably 20 to 50%, especially preferably 30 to 40%; and in a special way preferably 35% is contained in the entire process gas, the oxygen in a proportion of 39 to 98%, preferably 40 to 90%, particularly preferably 55 to 75%; and in particular Way preferably 60% is contained in the entire process gas, and the silicon-containing process gas is contained in a proportion of 0.5 to 1.5 element percent in the entire process gas, wherein the container has a coating thickness of 0.5 nm to 500 nm, preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and most preferably 75 nm, and / or the container has a wall thickness of 1 mm to 8.5 mm, preferably 2 mm to 5 mm, particularly preferably 3 mm to 4.5 mm, and most preferably 4 mm, and wherein the plastic container has an adhesive layer between the protective coating and the plastic substrate.

The plasma coating may be done as needed with the PICVD or the CVD method. Plasma enhanced chemical vapor deposition (PICVD), or PECVD or PACVD, is a special form of chemical vapor deposition (CVD) that promotes chemical deposition by plasma. The plasma can burn directly on the substrate to be coated (direct plasma method) or in a separate chamber (remote plasma method). The use of HMDSO and / or HMDSN surprisingly allows a particularly uniform and at the same time thin formation of the coating.

It is particularly advantageous if the coated container is obtainable by a method which is executable on the device described above.

Furthermore, it is advantageous if the plastic container polycyclic hydrocarbons and / or polycarbonates and / or polyesters and / or polyethylene terephthalates and / or polystyrene and / or polyethylene and / or HDPE and / or polypropylene and / or polymethyl methacrylate and / or PES and / or Polyolefins and / or Copolyester LX500 (TRITAN) and / or Copolyester EB062 (EASTAR) and / or Copolyester CN015 (EASTAR) and / or Copolyester LX101 (TRITAN) and / or Copolyester PN300 (Skygreen) and / or Copolyester T90G (ECOZEN) and Copolyester RN163C (UNIPET) and / or copolyester BR8040 (SKYPET) and / or copolyester AN014 (EASTAR) and / or copolyester EN076 (EASTAR) and / or copolyester AN004 (EASTAR).

Furthermore, it is advantageous if the plastic container is designed as a bottle or ampoule or carpule or syringe or dropper bottle or container for ointments or gels or perfume bottle.

The present object is moreover achieved by the invention providing a coated plastic container for storing aggressive and / or effective liquids and / or mixtures, wherein the container has a coating thickness of 0.5 nm to 500 nm, preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and most preferably has 75 nm, and / or the container has a wall thickness of 1 mm to 8.5 mm, preferably 2 mm to 5 mm, particularly preferably 3 mm to 4, 5 mm, and most preferably 4 mm, and the plastic polycyclic hydrocarbons and / or polycarbonates and / or polyester and / or polyethylene terephthalate and / or polystyrene and / or polyethylene and / or HDPE and / or polypropylene and / or polymethyl methacrylate and / or PES and / or polyolefins and / or copolyester LX500 (TRITAN) and / or copolyester EB062 (EASTAR) and / or copolyester CN015 (EASTAR) and / or copolyester LX101 (TRIT AN) and / or copolyester PN300 (Skygreen) and / or copolyester T90G (ECOZEN) and / or copolyester RN163C (UNIPET) and / or copolyester BR8040 (SKYPET) and / or copolyester AN014 (EASTAR) and / or copolyester EN076 (EASTAR) and / or copolyester AN004 (EASTAR), and wherein the plastic container has an adhesive layer between the protective coating and the plastic substrate.

It has proven to be particularly advantageous if the plastic container is designed as a bottle or ampoule or carpule or syringe or dropper bottle or container for ointments or gels or perfume bottle.

The present invention shows the surprising advantage that it is now possible to provide plastic containers which have advantageous properties when applied to products with alkaline and / or protein-based active substances and / or products with surface-active surfactants and / or unbuffered medicament solutions and / or acidic or neutral or basic formulations containing in particular at least one surfactant or surfactant and / or solutions in which a surfactant, that is a surfactant, consists of polysorbate and / or solutions containing sugars or sugar alcohols. The coated glass containers available in the prior art showed delamination phenomena when filled with aggressive or highly effective substances. The plastic containers available in the prior art showed high quality losses under the influence of aggressive or highly effective substances, which caused the wall of the plastic material to cloud and change its physical properties such as breaking strength and stability. In the context of the present invention, such changes in the plastic structure are also referred to as corrosion. Such corrosion phenomena Under certain circumstances, they can also lead to changes in the contents with regard to their optical properties and / or their taste and / or their odor. By providing a coated plastic container for storage of corrosive and / or effective liquids and / or mixtures, the invention provides a container which has no corrosion that could compromise the quality of the plastic bottle.

Surprisingly, it could be shown within the scope of the invention that it is now possible to inexpensively produce high-quality plastic containers with a high weight, which at the same time have a physical resistance to aggressive or highly effective substances comparable to glass containers, but have a glass-like properties. Thus, the present invention provides corrosion protection.

The present invention has also surprisingly overcome the problem found in the prior art that plastic bottles filled with aggressive or highly effective substances lose their transparency and / or their impact resistance by physical reaction with these liquids and / or become brittle. The impairment of the optical quality of plastic bottles by aggressive or highly effective liquids is also referred to as whitening, which means that the plastic bottles develop on their inside a whitish appearing turbidity.

The device according to the invention thus effectively prevents the disadvantages of the plastic containers available in the prior art, which could restrict their use.

As a result, a significant improvement over the prior art is achieved.

It is advantageous if the element for applying a negative pressure to the container and / or the element for introducing a process gas into the container is a gas lance.

In the context of the present invention, it has surprisingly been possible for the first time to show that the materials selected allow particularly thick wall thicknesses and thus that the plastic containers are similar in design and weight to glass containers. Thus, it could be shown in the context of the present invention that by using these materials it is now possible to produce vessels with a particularly high wall thickness, which remain transparent despite filling with highly effective and / or aggressive liquids and retain their physical properties and those of the product , Thus, it is possible, despite the use of plastics for the consumer to produce the high-quality visual and haptic impression of glass, and at the same time to ensure the breaking strength during use.

It is particularly advantageous if the container is made of a transparent material. This makes it possible for the consumer to give the high-quality visual impression of a glass vessel and at the same time to take advantage of a plastic vessel. Furthermore, it is advantageous if these containers are produced in various production processes, in particular plastic injection molding processes and / or injection blow molding and / or extrusion blow molding and / or injection stretch blow molding.

• 1 zeigt eine Vorrichtung gemäß der Erfindung zum Beschichten eines Kunststoffbehälters.
• 2 a und 2 b zeigen Aufnahmen aus der unbeschichteten Mitte einer Flasche, die mit einem Rasterelektronenmikroskop aufgenommen wurden.
• 3 a und 3 b zeigen Aufnahmen eines Flaschenbodens mit einem Rasterelektronenmikroskop.
• 4 zeigt eine glasähnliche zylindrische Flasche aus dickwandigem Kunststoffmaterial.
• 5 zeigt eine glasähnliche ovale Flasche aus dickwandigem Kunststoffmaterial.
• 6 zeigt Tiegel und Flaschen verschiedener Formen aus dickwandigem Kunststoffmaterial.

It has proven to be advantageous if the container is designed as a bottle or ampoule or carpule or syringe or dropper bottle or container for ointments or gels or perfume bottle.

• 1 shows a device according to the invention for coating a plastic container.
• 2 a and 2 B show images taken from the uncoated center of a bottle taken with a scanning electron microscope.
• 3 a and 3 b show pictures of a bottle bottom with a scanning electron microscope.
• 4 shows a glass-like cylindrical bottle of thick-walled plastic material.
• 5 shows a glass-like oval bottle of thick-walled plastic material.
• 6 shows crucibles and bottles of various shapes made of thick-walled plastic material.

The following example illustrates the surprising advantages of the invention.

Example:

The exemplary application example demonstrates that the device enables the production of containers which, even when in contact with aggressive or highly effective substances, have substantially less quality losses than the containers available in the prior art.

To test the extent to which the coating according to the invention is resistant to aggressive liquids, coated containers with liquids having different pH were investigated.

1. Determination of the sodium leaching after autoclaving for 6.2 hours at 121 ° C with different buffer systems (sealed containers, filling volume 12 ml).

2. Determination of the silicon leaching after autoclaving for 1.7 hours at 121 ° C with different buffer systems (sealed containers, filling volume 12 ml).

1. A.: pH 1: HCL c = 0,1 mol/L
2. B.: pH 7: Tris(hydroxymethyl)-aminomethan/Maleinsäure-Puffer, mit KOH eingestellt auf pH 7
3. C.: pH 9: Tris(hydroxymethyl)-aminomethan-Puffer, mit HCL eingestellt auf pH 9.

The determination of the sodium or silicon leaching was carried out according to ISO 4802-2 , The following buffer systems were used:

1. A .: pH 1: HCL c = 0.1 mol / L
2. B .: pH 7: tris (hydroxymethyl) -aminomethane / maleic acid buffer, adjusted to pH 7 with KOH
3. C: pH 9: tris (hydroxymethyl) aminomethane buffer, adjusted to pH 9 with HCl.

A .: The leaching values for sodium at 0.1M HCL were 0.035 and 0.052 respectively; the corresponding values for silicon were 0.16 and 0.08, respectively. For comparison, the leaching values for uncoated containers were 2.65 and 6.27, respectively.

B: Leaching levels of sodium at TRIS pH 7 were 0.00 and 0.01, respectively; the corresponding values for silicon were 0.07 and 0.05, respectively. For comparison, the values of leaching for uncoated containers were 0.45 and 1.55, respectively.

C: Leaching levels of sodium at TRIS pH 9 were 0.03 and 0.01, respectively; the corresponding values for silicon were 0.05 and 0.06, respectively. For comparison, the leaching values for uncoated containers were 0.70 and 2.24, respectively.

• 1 zeigt eine Vorrichtung gemäß der Erfindung zum Beschichten eines Kunststoffbehälters.
• 2 a und 2 b zeigen Aufnahmen mit dem Rasterelektronenmikroskop (REM). 2 a zeigt Aufnahmen aus der Flaschenmitte eines unbeschichteten Gefäßes in 250-facher Vergrößerung. Deutlich zu erkennen sind Rissbildung und lokales Quellen des Materials. Diese Veränderungen wurden durch Befüllung mit einer aggressiven Flüssigkeit hervorgerufen. Optisch führen diese Mikrorisse zu Eintrübungen, die optisch als Eintrübungen wahrgenommen werden. 2 b zeigt die Veränderungen in 50.000-facher Vergrößerung.
• 3 a und 3 b zeigen in 250-facher Vergrößerung REM-Aufnahmen. 3 a zeigt Aufnahmen der Flaschenmitte. Ausgehend von feinen Rissen bilden sich Reliefstrukturen durch Unterwanderung und Schädigung des Grundmaterials. Deutlich zu erkennen auf 3 b sind feine Rissnetzwerke und ähnliche Reliefstrukturen, die sich unter Einwirkung einer aggressiven Probeflüssigkeit auf dem Flaschenboden ausgebildet haben.
• 4 zeigt eine glasähnliche zylindrische Flasche aus dickwandigem Kunststoffmaterial.
• 5 zeigt eine glasähnliche ovale Flasche aus dickwandigem Kunststoffmaterial. Durch die dickwandige Beschaffenheit vermittelt die Flasche eine glasähnliche Optik.
• 6 zeigt Tiegel und Flaschen verschiedener Formen aus dickwandigem Kunststoffmaterial. Die Kunststoffbehälter in 5 bis 6 zeigen durch ihre großen Wandstärken das hochwertige Erscheinungsbild von Glasbehältern.

The test results show that the coating according to the invention makes it possible to coat containers in such a way that they are resistant to aggressive and highly effective liquids.

• 1 shows a device according to the invention for coating a plastic container.
• 2 a and 2 B show pictures with the Scanning Electron Microscope (SEM). 2 a shows images from the center of the bottle of an uncoated vessel at 250x magnification. Clearly visible are cracking and local swelling of the material. These changes were caused by filling with an aggressive fluid. Visually, these microcracks lead to clouding, which are perceived visually as opacities. 2 B shows the changes in 50,000 times magnification.
• 3 a and 3 b show SEM images at 250x magnification. 3 a shows pictures of the center of the bottle. Starting from fine cracks, relief structures are formed by infiltration and damage to the base material. Clearly visible 3 b are fine fracture networks and similar relief structures that have formed under the action of an aggressive sample liquid on the bottom of the bottle.
• 4 shows a glass-like cylindrical bottle of thick-walled plastic material.
• 5 shows a glass-like oval bottle of thick-walled plastic material. The thick-walled texture gives the bottle a glass-like appearance.
• 6 shows crucibles and bottles of various shapes made of thick-walled plastic material. The plastic container in 5 to 6 show through their large wall thicknesses the high quality appearance of glass containers.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102012110131 A1 [0002]
• US 4552791 [0004]
• DE 4438359 C2 [0005]

Cited non-patent literature

• ISO 4802-2 [0032]

Claims (8)

Device for carrying out a plasma coating of a plastic container, the device comprising a station frame (1) with handrails (2), a plasma chamber (3), a carriage (3) for holding a chamber wall (5), an element for applying a negative pressure to the container (6), an element for introducing a process gas into the container, a holding element (7) for fixing the container (6) to be treated, a microwave generator (8), and an adapter (9) which is connected via a coupling channel (10) to the plasma chamber (3), wherein the plasma chamber (3) comprises a chamber lid (11) comprising a flange (12) with a seal (13) enabling sealing of the chamber wall (5) relative to the chamber lid (11). Device after Claim 1 wherein the element for applying a negative pressure to the container (6) and / or the element for introducing a process gas into the container (6) is a gas lance. Coated plastic container obtainable by a coating process comprising the following steps: Inserting a container (6) into a plasma chamber (3), Sealing the chamber wall (5) by a flange (12) on a chamber lid (11), Applying a negative pressure to a container (6), Introducing the process gas into the container (6), Igniting a plasma by means of irradiated electromagnetic energy in the process gas introduced, wherein the coating comprises at least one silicon compound as well as argon and Contains oxygen, the argon in a proportion of 10 to 60%, preferably 20 to 50%, particularly preferably 30 to 40%; and in a special way preferably 35% is contained in the entire process gas, the oxygen in a proportion of 39 to 98%, preferably 40 to 90%, particularly preferably 55 to 75%; and in a special way preferably 60% is contained in the entire process gas, and the silicon-containing process gas is contained in a proportion of 0.5 to 1.5 element percent in the entire process gas, wherein the container has a coating thickness of 0.5 nm to 500 nm, preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and most preferably 75 nm, and / or the container has a wall thickness of 1 mm to 8.5 mm, preferably 2 mm to 5 mm, particularly preferably 3 mm to 4.5 mm, and in a very special way preferably 4 mm, and wherein the plastic container between the protective coating and the plastic substrate has an adhesive layer. Plastic container after Claim 3 , obtainable by a method based on a device Claim 1 or 2 is executable. Plastic container according to one of the preceding claims, wherein the plastic comprises polycyclic hydrocarbons and / or polycarbonates and / or polyesters and / or polyethylene terephthalates and / or polystyrene and / or polyethylene and / or HDPE and / or polypropylene and / or polymethyl methacrylate and / or PES and / or polyolefins and / or copolyesters LX500 (TRITAN) and / or copolyester EB062 (EASTAR) and / or copolyester CN015 (EASTAR) and / or copolyester LX101 (TRITAN) and / or copolyester PN300 (Skygreen) and / or copolyester T90G (ECOZEN) and / or copolyester RN163C (UNIPET) and / or copolyester BR8040 (SKYPET) and / or copolyester AN014 (EASTAR) and / or copolyester EN076 (EASTAR) and / or copolyester AN004 (EASTAR). Plastic container according to one of the preceding claims, wherein the container is designed as a bottle or ampoule or carpule or syringe or dropper bottle or container for ointments or gels or perfume bottle. Coated plastic container for storing aggressive and / or effective liquids and / or mixtures, wherein the container has a coating thickness of 0.5 nm to 500 nm, preferably 1 nm to 200 nm, more preferably 5 nm to 100 nm, and in a very special way Preferably, 75 nm, and / or the container has a wall thickness of 1 mm to 8.5 mm, preferably 2 mm to 5 mm, more preferably 3 mm to 4.5 mm, and most preferably 4 mm, and the Plastic polycyclic hydrocarbons and / or polycarbonates and / or polyesters and / or polyethylene terephthalates and / or polystyrene and / or polyethylene and / or HDPE and / or polypropylene and / or polymethylmethacrylate and / or PES and / or polyolefins and / or copolyester LX500 (TRITAN ) and / or copolyester EB062 (EASTAR) and / or copolyester CN015 (EASTAR) and / or copolyester LX101 (TRITAN) and / or copolyester PN300 (Skygreen) and / or copolyester T90G (ECOZEN) and / or copolyester RN163C (UNIPET) and / or copolyester BR8040 (SKYPET) and / or copolyester AN014 (EASTAR) and / or copolyester EN076 (EASTAR) and / or copolyester AN004 (EASTAR), and wherein the plastic container has an adhesive layer between the protective coating and the plastic substrate , Plastic container after Claim 7 wherein the container is designed as a bottle or ampoule or carpule or syringe or dropping bottle or container for ointments or gels or perfume bottle.

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