WO2001002269A1

WO2001002269A1 - Compressed gas container and use thereof

Info

Publication number: WO2001002269A1
Application number: PCT/EP2000/006198
Authority: WO
Inventors: Volker Herzog; Udo Kohn; Franz Steigerwald
Original assignee: Wella Aktiengesellschaft
Priority date: 1999-07-01
Filing date: 2000-07-03
Publication date: 2001-01-11
Also published as: AU5823700A; JP2003503289A; DE10031136A1

Abstract

The invention relates to a compressed gas container (1) and to the use thereof. Said container comprises an extraction valve (2) for storing and releasing a foaming hair dye product. A drawn compressed gas container (1) consisting of plastic is provided. This container is blown and drawn from an injected preform in a thermoelastic state into a final form. The plastic used is polyethyleneterephthalate (PETP) or polyethylenenaphthalate (PEN) or an optional mixture of PETP and PEN. The inventive compressed gas container (1) is drawn 1:1.3 to 1:3.0 in a radial direction and 1:1.15 to 1:2.0 in an axial direction and has an outer wall thickness (D) of 0.4 to 1.3 mm for a container volume of 20 to 200 ml.

Description

Pressurized gas container and use of the pressurized gas container

The invention relates to a pressurized gas container and a use of the pressurized gas container for storing and dispensing a foamable hair dye product.

A large number of different basic formulations are used for hair dyes. For oxidative or direct formulations, cationic, anionic or non-ionic base formulations are used, which are acidic or alkaline depending on the area of application. In particular, ammonia or aliphatic amines such as monoethanolamine are used as alkalizing agents. Hair dyes are usually packaged in containers made of aluminum, glass, PVC, PET or glycol-modified PET due to their requirements for the packaging materials. In particular, containers made of PET and glycol-modified PET show embrittlement symptoms as a result of interactions after a certain period of storage, so that the containers no longer meet the requirements for stability. Will the

Hair coloring products manufactured as aerosol formulations in which a liquefied propellant such as e.g. Propane / butane is used, the requirements for the safety and stability of the container increase. For this reason, compressed gas containers made of internally coated aluminum have been used for this purpose.

Aerosol containers or pressurized gas containers made of plastic are known, but they have not yet been used for chemical or hair color changing agents. If such containers are used for packaging the hair color-changing agents in pressurized gas containers, the interactions and embrittlement phenomena lead to considerable

Safety risks, in particular that the same bursts explosively when the container falls. This can be seen in storage tests with an increased

Temperature of 40 ° C, where after three months of storage State-of-the-art plastic containers, e.g. made of PET, burst in the drop test as a result of these interactions.

Bio-oriented containers made of PET are known for the storage of gas-containing and gas-free beverages, but on which much lower demands are placed on the chemical inertness of the container material. As a rule, these are neutral to acidic liquids, which may contain only slight traces of food coloring and therefore place far less demands on the container and material.

It is obvious to a person skilled in the art to refrain from such a PET container in the case of filling goods with higher requirements for chemical resistance and mechanical strength, since experience has shown that slightly stronger influences on the material lead to a considerable reduction in the properties for a pressure container. Attempts to store undiluted containers clearly confirm this conclusion.

For hair dyes in particular, only PVC has proven to be an almost unconditionally suitable material apart from glass.

Stretch-blown containers, whose wall thicknesses reach an excessively high range of 2-3 mm, lead to unsatisfactory wall thickness distributions depending on the container mouth and outer container dimensions.

If, for reasons of stability, high wall thicknesses of 2-3 mm are required, this results in preform wall thicknesses which are no longer technically manageable in the heat balance of the preform for the stretch blow molding process and which lead to unsatisfactory inflation processes to the final container. This is particularly noticeable in the design-related dimensional ratios of the desired container with a mouth diameter suitable for a 20 mm aerosol valve mouth with an outer diameter of 30 mm and 94 mm container length. Hair dyes of the type described have therefore previously only been packed as compressed gas containers in aluminum cans, since all requirements can be met here.

Recently, however, it has become necessary to make the cosmetic effectiveness and the hair dye product range clearer to the consumer, also through emotionally effective packaging properties. Here, aluminum compressed gas cans have the considerable disadvantage that they are known to consumers as a standard packaging material for a wide range of content, even outside of cosmetics, and convey less of an impression of a cosmetic product. In addition, aluminum pressure gas cans give an uncomfortable feeling of cold when touched by hand.

Plastic materials for packaging hair dye are limited to a few materials due to the above requirements or cost necessities. These are the plastics PVC and PET. PVC is not available due to its negative environmental properties, so PET is the only available plastic. It is also known here that PET containers do not satisfactorily meet the requirements for packaging for hair dyes. This is shown by a first example of a PET container with a hair coloring product that was produced in a single-axis stretch blow molding process: filling quantity 70 ml, rectangular cross-section. Description of the case values after storage with colorant at 20 ° C and 12 months:

Breakage in approx. 20% of the containers from a fall height of 1.8 m.

Second example of a PET container with a hair coloring product in aerosol form, which was produced by uniaxially stretched injection blow molding and is designed as a compressed gas container:

Mouth edge diameter = 20mm, container diameter = 30mm, length = 100mm, internal volume: 50ml, filling volume: 40 ml, wall thickness distribution: 0.8 to 1.3 mm. Storage conditions: 0 months 20C ° 6 months 40C ° 12 months 20C °

Fall test results 1, 80m: 0% break 50% break 20% break

(explosive) (explosive)

Traction until break: 320N 270N 264N

Elongation at break: 90% 10% 10%.

In the case of broken containers, the consumer is at risk from bursting and splintering of the container and from splashing of the product. At the same time, property damage is caused by pollution of the environment. The tensile / elongation values determined on container cutouts show that this material has become embrittled after the storage test, so that the above case values can be understood.

A larger pressurized gas container - as a third example - in the volume range around 150 ml, which was made from PET, showed comparable behavior.

Description of the container:

Muzzle edge diameter = 25.5 mm,

Body diameter = 35 mm,

Length = 135 mm, internal volume = 180 ml,

Wall thickness distribution from 0.6 mm to 1.1 mm.

According to these results, the expert must assume that the use of a PET container as a pressure container for packaging a hair dye as aerosol foam is not possible.

It is therefore an object of the invention to provide a pressurized gas container or a use of a pressurized gas container made of plastic, which is suitable for storing an above-described hair color-changing product and for dispensing the product in foam form and is inexpensive to produce and does not have the aforementioned disadvantages, which in particular have no safety risks (Risk of bursting, falling resistance) and is largely chemically inert. The secondary task relates to a pressurized gas container or to the use of a pressurized gas container made of plastic, which has satisfactory properties in order to safely store a hair dye as a foamable product in accordance with the requirements of the German regulation Technical Regulations for Compressed Gases TRG300, while ensuring product safety and product suitability of at least 30 Months. These are containers for less than three applications with a filling volume of up to 35 ml and an internal volume of up to 50 ml. An essential criterion of the TRG300 as well as a corresponding consumer safety is the so-called drop resistance. Here it must be ensured that a pressurized

Container withstands a fall from 1.8 m height without damage and bursting. The hair dye is mixed with LPG of the propane / butane type under an internal pressure of 2.7 bar inside the container, which internal pressure can rise to 3.7 bar when heated to 50 ° C. At the same time, there is an interaction between the hair dye and the material of the plastic container, which can lead to embrittlement. It has been found that hair dyes in particular, due to their pH value (> 7) and their content of color pigments due to the chemical attack and also due to the migration of the color pigments, can have a particularly strong influence on the mechanical properties of a plastic over the course of an interaction period. On the other hand, a high diffusion tightness of the plastic against oxygen must be ensured at the same time, so that there is no premature oxidation of the hair dye. A minimum requirement of approx. 0.04 • 10 ³ cm ³ • cm • -2 • -1 • -1 Pa has proven to be necessary here. Furthermore, the TRG300 demands that the

Product life of such a container resists a bursting pressure of> 12 bar at 20 ° C.

Another subordinate task is to create a pressurized gas container or a use of a pressurized gas container for a cosmetic agent, which represents a characteristic new signal for the cosmetic product category of hair dye or hair tint as aerosol foam. This object is achieved according to the features of claim 1 or according to the features of the independent claim 8. Further advantageous developments of the invention emerge from the respective subclaims.

The fact that a pressurized gas container with a removal valve for storing and dispensing a foamable hair dye product, a stretched pressurized gas container made of plastic is provided, which is inflated and stretched as a molded preform in a thermoelastic state and that the plastic is polyethylene terephthalate (PETP) or Polyethylene naphthalate (PEN) or an optional mixture of PETP and PEN is provided that the pressurized gas container in the radial direction in a range of 1: 1, 3 to 1: 3.0 and in the axial direction in a range of 1: 1, 15 to 1: 2.0 is stretched, and that a jacket wall thickness in a range of 0.4 to 1.3 mm is provided with a container inner volume of 20 to 200 ml, a pressure gas container made of plastic is now created after the task, which is excellent for a Use of a hair color changing product described above for storing and dispensing the product in S foam shape is suitable.

With the use of the pressurized gas container according to the invention, the safety requirements in the form of the required drop resistance at 1.8 m drop height are also met (drop without break). Surprisingly, the negative effects of the interactions between the hair dye or chemical products, which are particularly due to pigment migration and pH values, are prevented. In addition, there is a high burst strength at room temperature with a high internal pressure. Even after a six-month storage test at 40 degrees Celsius, the burst strength and drop resistance of the pressure vessels were retained. 30 to approximately 200 ml can be provided as the filling volume. With a filling volume of 30 to 125 ml, a wall thickness of approximately 0.8 mm has proven itself. The pressure vessel is preferably stretched approximately 1: 1, 7 in the radial direction and 1: 1, 2 in the axial direction. Direct hair colors based on toning agents in the acidic / alkaline range or cationic or anionic or oxidative hair colors based on oleic acid or monoethanol or ammonia as alkalizing agents are suitable as hair colorants suitable. Another advantage is that the respective fill level of the agent in the transparent pressure vessel is visible from the outside.

In a preferred embodiment, the compressed gas container is stretched approximately 1: 1, 7 in the radial direction and 1: 1, 2 in the axial direction. With a 40 ml pressurized gas container, the preform had a length of 83 mm and an outer diameter of 17 mm. After inflation, the compressed gas container had a length of 95 mm and an outer diameter of 30 mm, which corresponds to an axial stretching of 1: 1, 15 and a radial stretching of 1: 1, 76. The axial stretching of the preform into one

Compressed gas containers are made mechanically by means of a stamp which is guided through the container opening of the preform, which is heated to approximately 80 degrees, to the inside bottom of the container and then presses axially onto the bottom. At the same time, the preform is inflated under a pressure of approximately 30 to 40 bar, with the preform being radially stretched at the same time, resulting in such a molecular stretching which leads to the required chemical resistance and the required pressure resistance.

1 shows an enlarged illustration of an exemplary embodiment of a pressurized gas container 1 according to the invention made of plastic with the following values:

Container diameter A = 30 mm,

Container length B = 94 mm,

Mouth edge diameter C = 20 mm, filling volume = approx. 40 ml,

Internal volume = approx. 50 ml,

Wall thickness distribution D from 0.8 mm to 1.3 mm, radial stretching: 1: 1, 7, axial stretching: 1: 1, 2, ratio of container diameter A to container length B: 1: 3.2.

The container mouth E serves as a crimp rim F for a small valve (tilting valve) 2 indicated by a broken line with an actuating attachment 3 (FIG. 2). A container base G is designed as a hemisphere base H, which optionally also places a valve protection cap 4 (FIG. 2) indicated by a broken line on the hemisphere base H is made possible by optionally a cap receiving seat I (FIG. 2), which brings about additional fall protection and easier handling in the state of an application and the container 1 can also be placed upright. Two-component packaging 1, 1 (not shown) arranged next to one another enables two-component packaging to be implemented, with a mixing element (not shown) being assigned to the two dispensing valves 2, 2.

Results of the following tests show the progress of the technical properties as a result of the design according to the invention:

Storage conditions: 0 months 20C ° 6 months 40C ° 12 months 20C °

Fall test results 1.80m: 0% break 0% break 0% break

Tensile force to break: 333N 326N 322N Elongation to break: 90% 90% 90%

These results prove that such a pressurized gas container for hair dye surprisingly meets the requirements described above.

Here, plastic is shown to be outstandingly suitable as a compressed gas container material, as is already used in a variety of ways in unpressurized plastic cosmetic containers. The warm grip, the freer design options, the transparency and the optional coloring of the plastic material have ideal conditions for a cosmetic-looking compressed gas container.

The invention surprisingly shows that it is possible to use a compressed gas container made of plastic with a targeted selection with regard to design and stretching conditions, which satisfactorily fulfills the requirements set by the task, so that this is one from the perspective of the consumer new type of cosmetic product could be created. Reference list:

A tank diameter

B container length

C Muzzle edge diameter D jacket wall thickness or jacket wall thickness distribution

E tank mouth

F crimped edge

G container bottom

H hemisphere bottom I cap seat

1 compressed gas tank

2 dispensing valve (tilting valve)

3 Valve cap actuating attachment

Claims

claims

1. compressed gas container (1) with a removal valve (2) for storing and dispensing a foamable hair dye product, wherein a stretched compressed gas container (1) is provided made of plastic, which is inflated and stretched into a final shape as a molded preform in a thermoelastic state that as a plastic polyethylene terephthalate (PETP) or polyethylene naphthalate (PEN) or an optional mixture of PETP and PEN is provided that the pressure gas container (1) in the radial direction in a range of 1: 1, 3 to 1: 3.0 and in the axial direction is stretched in a range from 1: 1, 15 to 1: 2.0, and that a jacket wall thickness (D) is provided in a range from 0.4 to 1.3 mm with an inner container volume of 20 to 200 ml.

2. Pressurized gas container according to claim 1, characterized in that the pressurized gas container (1) is stretched in the radial direction by approximately 1: 1, 7 and in the axial direction by approximately 1: 1, 2.

3. Pressurized gas container according to claim 1, characterized in that a jacket wall thickness distribution (D) of approximately 0.8 to 1.3 mm is provided with a container inner volume of approximately 50 ml.

4. Pressurized gas container according to claim 1, characterized in that direct hair colors based on toning agents in the acidic / alkaline range or cationic or anionic or oxidative hair colors based on oleic acid or monoethanol or ammonia are provided as alkalizing agents.

5. Pressurized gas container according to claim 1, characterized in that a container base (G) is designed as a hemispherical base (H) with a receiving seat (I) for a valve protection cap (4).

6. Pressurized gas container according to claim 1, characterized in that the pressurized gas container (1) consists of transparent, optionally made of colored plastic.

7. Pressurized gas container according to claim 1, characterized in that two pressure gas containers (1, 1) arranged next to one another are provided as a two-component packaging.

8. Use of a pressurized gas container (1) with a removal valve (2) for storing and dispensing a foamable hair dye product, a stretched pressurized gas container (1) made of plastic being provided, which is inflated and stretched as a molded preform in a thermoelastic state that as plastic polyethylene terephthalate (PETP) or polyethylene naphthalate (PEN) or an optional mixture of PETP and PEN is provided that the compressed gas container (1) in the radial direction in a range of 1: 1, 3 to 1: 3.0 and in axial direction is stretched in a range of 1: 1, 15 to 1: 2.0, and that a jacket wall thickness (D) is provided in a range of 0.4 to 1, 3 mm with a container inner volume of 20 to 200 ml.

9. Use according to claim 8, characterized in that the compressed gas container (1) is stretched in the radial direction approximately by 1: 1, 7 and in the axial direction approximately by 1: 1, 2.

10.Use according to claim 8, characterized in that a

Sheath wall thickness distribution (D) of approximately 0.8 to 1.3 mm is provided with a container inner volume of approximately 50 ml.

11. Use according to claim 8, characterized in that as

Hair coloring product direct hair colors based on tinting agents in the acidic / alkaline range or cationic or anionic or oxidative Hair colors based on oleic acid or monoethanol or ammonia are provided as alkalizing agents.

12. Use according to claim 8, characterized in that a container bottom (G) is designed as a hemisphere bottom (H) with a receiving seat (I) for a valve protection cap (4).

13. Use according to claim 8, characterized in that the compressed gas container (1) consists of transparent, optionally made of colored plastic.

14. Use according to claim 8, characterized in that two pressure gas containers (1, 1) arranged next to one another are provided as a two-component packaging.