BG98497A - Container for the storage and distribution of aromatized or perfumed product, water-containing, for example - Google Patents

Abstract

The subject of the invention is a storage and dispensing (distribution) tube (C) for a product, for example a water-containing product which may be flavoured or perfumed, comprising a dispensing head which is fixed onto a flexible multilayer skirt, this skirt essentially containing an intermediate polymer layer (20) which has a barrier effect with respect to oxygen and flavours or perfumes, the said layer being sensitive to humidity, as well as, on each face of this intermediate layer, one or more polymer layers (1; 12,14,10) based on polyolefins, all of the said layers being bonded together in a continuous manner, characterised in that the set of layers situated on the inner face of the said intermediate layer having a barrier effect (1,21) has a total thickness of between 40 and 150 micrometres, so as better to conserve the flavour or the perfume which is or may be contained therein. This tube preferably includes one or two means which render the dispensing of the contained product easier and more complete. It applies to the industries for packaging products which are, for example, liquid, creamy or pasty. <IMAGE>

Description

The invention relates to a container for storing and distributing products that are usually liquid, creamy or pasty. This container allows the aroma or perfume of the contained product to be well stored.

EP-A-0084 922 and U.S. Patent 4,626,456 recognize a container for storing and distributing a product, for example a flavored or perfumed, water-containing product, the container having an overhead serving to be fixed to a multilayer flexible body, such as the body contains essentially an intermediate layer that serves as a barrier to oxygen and essences or fragrances. This layer is sensitive to moisture and one or more opiolefin-based polymer layers are located on each side of this intermediate layer, all of which are interconnected. For example, if the contents of the container are toothpaste, the intermediate layer as a barrier is, for example, a copolymer of ethylene and vinyl alcohol. The structure of the body, without the intermediate layer consisting of layers of polypropylene, dusted with, for example, calcium carbonate, mica or talc, makes it possible to achieve a good protection of the container from breaking when folded.

There are two drawbacks to such a container.

On the one hand, and this is known, for example, in U.S. Patent 4,407,897, the copolymer of ethylene and vinyl alcohol is very sensitive to moisture. A toothpaste contains 20 to 50% moisture permanently in the mass, and a large loss of the aroma of the paste is found in the multi-layer containers with a barrier layer of ethylene-vinyl alcohol copolymer.

In addition, partial breakage of the container tubes is found to be difficult to empty.

British Patent A-2048209 discloses a container for a product such as toothpaste whose multilayer plastic body is deformable when pressed sequentially and is non-adhesive between layers. This body contains at least one layer as a barrier with respect to oxygen from a copolymer of ethylene and vinyl alcohol or polyamide, one layer of olefin and one layer of adhesive (modified) olefin located before the other two layers. The adhesion between the layers is avoided by a marginal elasticity of the adhesive layer, which is weaker than that of the barrier layer and greater than that of the olefin layer.

At the same time, the density of the olefin layer is greater than the sum of the densities of the barrier and adhesive layers, and the result of the elastic density of the olefin layer is 7 to 170 kg / cm. These tools improve deformation and recovery after each container container is pressed. This document does not indicate how to avoid the loss of aroma found by the lack of adhesion between the layers of the body of the container.

The applicant has set himself the task of securing a container,

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ensuring the best preservation of the essence or aroma of the product contained in the container. In addition, a container is sought, which makes the transfer of the product easier and more complete.

The invention is intended for such a container, known from the above-mentioned materials, characterized in that the integrity of the layers located on the inside of the interlayer in question with a barrier effect has a total density of between 40 and 150 micrometers, allows to maintain the aroma or odor of a product that is or will be contained in the container.

The applicant's rationale in this area is the following: when the density of the above-mentioned layers located on the inside of the barrier layer is less than 40 micrometers, the humidity of the product passing through these layers begins to rapidly deteriorate the properties of the barrier layer in terms of oxygen and fragrances, these fragrances of the product can pass through this layer and even be lost.

When the density of the layers is greater than 150 micrometers, the humidity does not reach the intermediate layer with a barrier effect in sufficient quantity to spoil its properties, but the aromas are absorbed and retained in sufficient quantity through these said layers. These fragrances are typical constituents of an aqueous solution contained in a product, and its evaporation and absorption follow approximately the evaporation and absorption of the water forming the humidity of the product.

The material A-2 048 209 does not allow to predict these effects, despite their importance, nor does it provide any direct or indirect indication of the density of the layers located on the inside of the barrier layer.

The best results for preserving the aroma of the product you find in the container are achieved when the total density of the layers located on the interlayer with a barrier effect has reached between 55 and 140 micrometers and is rather between 65 and 1J0 micrometers , the most favorable being 70 to 120 micrometers.

The foregoing conditions allow them to be used to build an economical polyolefin body and provide perfect adhesion of the layers to one another, knowing the polyethylene properties. The applicant is also interested in a container in which the polymer layers based on the body polyolefin consist, on one side, of a low or very low specific gravity or linear low density polyethylene surface layer having a specific mass reaching between 0.86 and 0.957 g / cm ³ and, on the other hand, other layers, which are respectively of low specific gravity polyethylene (PE.BD), specific mass reaching between 0,90 and 0,95 g / cm ³ or high specific gravity polyethylene (PE.HD) specific mass between 0.955 and 0.97 g / cm ^? .

Wanting to make it easier and more complete to distribute the product contained in the inventive container that best preserves the aroma of this product, the applicant has found that local breakage due to the pressure of the container could be avoided, such as improve elasticity when pressed on the body. Therefore, the polyethylene layers of the container body comprise one or more layers of polyethylene with a high specific gravity pe.hd having a total density greater than or equal to 90 micrometers. Tests show that when the total density of pe.hd passes in the range of 84

Shi * up to 125 micrometers, the force of the elastic response of the body when pressed is more than double. When the body density is between 260 and 500 micrometers, for example in the case of a toothpaste container, the said total density of layers of high specific gravity polyethylene (PE.HD) is rather between 100 and 140 micrometers. The outer layers are preferably made of low specific gravity polyethylene (PE.BD) or have an inner layer of low linear density polyethylene.

In fact, for these outer layers, a good flexibility is sought with a good ability to press on the outside of the container-tube and good resistance to small cracks in the interior of the container. The boundaries between the overall density of high specific gravity polyethylene (PE.HD) which are advantageous are shifted relative to the density of the body if it is outside the specific limit. Consideration should be given to this increase in the elastic response of the container body to compression with respect to the influence of the intermediate barrier layer, which has higher characteristics than PE.HD at the same density. For the sheath density cited above, it is preferable that the sum of the 2 times the density of said barrier layer and the total density of the PE.HD high density polyethylene layers is between 150 and 180 micrometers, with the above condition being refers to the total density of PE.HD layers whether or not it is sufficient.

In order to facilitate production, having in mind the properties of the outer layers above, made exclusively of low-specific-weight PE.BD polyethylene, in order to achieve the overall density of pe.hd, it is desirable to use:

or a first layer of high-specification polyethylene

- 6 PE.HD solid weight, which is inserted between said outer and inner layers and one first intermediate layer of low-specific-weight polyethylene PE.BD, itself located inside the intermediate barrier layer;

- or one second layer of high-specificity polyethylene PE.HD which is inserted between one outer layer of low-specificity polyethylene and one second intermediate layer of low-specificity polyethylene PE.BD located externally at the intermediate barrier layer.

Thus, the first and second layers of high specific weight PE.hd polyethylene are convenient for simultaneous use

-D with a density of 10 and 50 micrometers and 60 and respectively

140 micrometers.

This layer or these layers of high-specific-weight PE.HD polyethylene are typically fabricated "in a continuous fusion with the layers between which they are embedded, with the materials of which they are made compatible in the fusion and in the manufacturing process a structure with excellent bonding time between layers is obtained. A layer of pe.hd embedded in this way can be seen on the cross section through a measure of microhardness, but not as a structure. The soldered layers thus obtained are obtained by double pouring the body or by brazing with the coating of the edges of the first multilayer layer, obtained by itself from one or several ** double rolls after joining, using a protective coating of molten polyethylene.

Usually, the first and second intermediate layers of polyethylene are each individually bonded to one side of the intermediate barrier layer and surrounded by a bonding layer, often by EAA or EMA. The five layers in question are often prepared in advance in the form of a multi-layer barrier in which

- The 7th layer, sensitive to moisture, is thus well protected.

As materials for moisture sensitive barrier layers, EVOH and PVOH can be cited, whose moisture damage is described in U.S. Patent 4,407,897, cited above, and has a sensitivity level lower than that of polyamides and altered polyamides, for example adinamide polymethaxylene (MHD6). One such barrier intermediate layer in the container body has an ordinary density between 0.001 and 0.05 mm and may have several barrier layers, preferably having the total density cited above.

In order to facilitate and more comprehensively distribute the product stored in the inventive container, the applicant proposes a second method that can be used alone or in combination with the first, imposing a minimum density of PE.HD layers on the container body, larger than 90 micrometers.

The second way is to have an elastic annular arm between the body and the opening of the container. It is known that the arm of known tubing containers, by the way they are manufactured, are rigid and form something like a wall holding a portion of the distribution product, the product being usually creamy or mushy. Due to the method of production which is the subject of French patent 95 01065 of 27.01.1995, the applicant thus obtains a preferred container in which the dispensing head comprises a neck smaller than the body and an annular arm connecting the neck to the body, such as this arm is flexible and has a density between 0.9 and 1.55 times faster

- 8 between 0.8 and 1.25 times the density of the body as a continuation of this structure, follows the body and the surrounding creased and soldered folds, the above-mentioned arm being easily foldable laterally. The cited arm, and especially the smallest part of the neck of the container, contain barrier layers of the body of the container in the form of folded and extended folds contained in the elastic and soldered folds mentioned above, which themselves are a continuation of said barriers layers of the body. The neck can be fitted with a ring made of polyethylene, soldered to the upper part, and the shoulders remain at least half elastic.

The second method offers at the same time the possibility of an easier and more complete distribution of the product contained in the container, as well as the preservation of its aroma improved at the level of the upper part of the container. The folds that tapering in the direction of the barrier layer in the arm generally satisfy the general preferred condition for an overall density of 0.01 to 0.05 mm with enhanced efficiency. The manufacturing process associated with this second method of container manufacturing will be described in detail in the examples.

Advantages of the invention:

- With the economical structure of the body it provides a much better way of preserving the aroma of the stored product

- allows, inter alia, the preferred features to limit partial damage to the container when pressed, with pressures acting on a wider part of the container and sometimes being facilitated

- in the alternative or in combination with the effect of limiting these damage to the body, the invention offers the possibility of easy lateral folding of the upper part, as well as

- 9 easier and more complete emptying of the product at the end of the distribution.

Examples:

Figures 1 to 5 show three containers in total, the first of which is outside the invention (Fig. 1 - control) and the other two (Figures 2 and 9) according to the invention.

FIG. 4 shows in axial section the distributional measure of the elastic reaction when pressed on the body of the container in connection with the first method of manufacture allowing the easier and more complete distribution of the product.

1 * · FIG. 5 is a graph showing the sample weight taken from the body of the container, depending on the total density of the inner layer of the barrier layer in the aroma loss test.

FIG. b shows graphically the variations in the flexural resistance of the body, depending on the total density of the high density PE.HD polyethylene layers used.

Figures 7 to 10 refer to the second improved workmanship for better distribution relating to an elastic arm. FIG. 7 shows the conditional perspective of the container obtained for comparison by the formation of the ambient temperature

FIG. 8 shows a container according to the invention having an elastic arm in axial section.

FIG. 9 shows another container with an elastic arm provided with a polyethylene annular crown that forms the outer part of the opening in an axial section.

FIG. 10 shows a micrograph of a view of the height of the container arm and the joining of the arms to the aforementioned annular crown by means of an axial section.

The body structures of the containers of Figures 1 to 5 show all three inner layers with barrier effect 20 of EVOH having a density of 0.02 mm, connected to two adhesive layers 21 and 22 of a copolymer EMA (ethylene copolymer and methacrylic acid) with a density of 0 , 01 mm, each of these layers of polyethylene coming into contact with these connecting layers 21 and 22 of PE.BD with a specific mass of 0.92 g / cm ² in layer 1 or in the inner layer 11 or 12. The boundaries of the layers

of different composition are marked by a solid line, while the invisible boundaries between the sub-layer pe.bd and PE.HD, the result of their joining in one solid state, at least in area, are marked with dashed lines.

The term sublayer is used herein to mean layers for which at least one bounded surface is invisible. However, these are layers exclusively for examining the technical features of the invention. They can be labeled with microhardness measures.

It can be seen from Figures 1 to 5 that the sub-layers of PE.HD 15 and 14 with a specific mass of 0.95 g / cm ² are located in each of the cited gaps under layers of pe.bd 11 or 12 and one sub-layer PE having an internal linear density of 100 or from pe.bd external 10.

Walking from the inside of the shell to its outside, the sequence of densities is described in detail, with the details of the sub-layers indicated in quotes:

Container A (Fig. 1): layer 1 - pe.bd- 0.055 mm; EMA 21 layers of 0.01 mm, EVOH 20 of 0.02 mm; EMA 22 of 0.01 mm; layer of PE 12 + 14 + 10 of 0.215 mm (PE.BD 12 of 0.082 mm, PE.HD14 of 0.0105 mm, pe.bd 10 - outer of 0.025 mm)

Container B (Fig. 2) - inner layer of PE '100 + 15 + 11' 'of 0.09 mm (PE - linear outer density 100 of 0.01 mm, PE.HD 15 of 0.02 mm, PE .BD11 of 0.06 mm), successively EMA, EVOH, EMA as in A, a layer of PE "12 + 14 + 10" of 0.215 mm of the same ingredient as in A.

Container C (Fig. 5) - inner layer 1 of PE.BD0.125 mm, sequentially EMA, EVOH, EMA act at A and B, layers of PE ”12 + 14 + 10” of 0.175 mm (PE.BD 12 of 0.075 mm, pe.hd 14 of 0.084 mm, PE.BD10 external of 0.018 mm).

The bodies of containers A, B, C are wound up and tightly coupled at the beginning with a barely perceptible film having the W * structure and density indicated above, and then the top of the containers is poured onto this body.

Aroma loss test.

50 mm diameter round sections of the above mentioned three types are shown. 1 to 5 of impregnation of the inner surface of the body, layer 1 or 100, of a standard toothpaste containing 25% water and menthol for 4 weeks at 58 ° C.

At the end of the test, the sample was cleaned of the toothpaste left on the surface. The weight taken determines the loss of water and aroma.

A quality is desired, which in this test gives a unit weight of less than 1.2 mg / cm ² and less than 0.66 mg / cm ² . This is satisfactory by the first criterion but not by the second. The test results are given in Table 1 and FIG. 5 ·

The explanation is this: there is no sample in which the barrier layer of EVOH is exposed on the inside of the body, because such a layer of EVOH will be completely damaged by humidity during the production of a similar multilayer layer. Note in FIG. 5 such a sample what a result of weight it produces - it is overestimated, due to the easy passage through the EVOH of moisture and the absorption of that moisture through the outer layers of the EVOH. After having 0.02 mm of EVOH inner layer, another significant point of weight, more than 2.5 mg / cm ² , is observed. The weight decreases rapidly because the density of the inner layers of EVOH exceeds 0.05 mm and part of the curve line and height at which A is located responds to an absorption with degradation of EVOH by moisture, then passes through these EVOH through water and aroma. , the moisture is also well absorbed by the outer layers of EVOH 21, 12, 14 and 10 compared to the inner layers 21 and 1. The decrease in A and B corresponds to a predominant protective effect of the 20 otEVOH layers by the increasing density of the inner layers and the ascent from B to C corresponds to the influence that occurred before having the absorption of water and aroma, the inner layers, their density and so also the absorption capacity is increased because EVOH protects well.

Body pressure test or resistance test.

A sample 15 of the body is brought to the position of a dome 16, a cylindrical semicircle, reproduced with a diameter of 25 mm and a length of 100 mm; we press it with a rigid lever 17 with a diameter of ** 5 mm, according to the linear 18 at the top of this dome. The dashed line drawing 19 shows the acquired shape of the dome 16, since the penetration of the lever 17 has a constant velocity.

A reference system (not shown) measures the counteraction of a dome 16 or 19 on a lever 17 and determines the maximum. Because the reaction is strong, the container body has an equally good pressure resistance

- 15 and its indentation remains partly at least in an elastic environment, avoiding local pressures contrary to the instructions in document EP-A-0 084 922.

The test results are summarized in Table 2 and FIG. 6. The points A, B, C, arranged in a straight line in Figure 6. When the reaction is absent from PE.HD in the body, then all PE.BD, except EVOH and the fine adhesive layers 21 and 22 that surround it, is less positive (figurative point Z); the effect of density is seen to increase from PE.HD on the body's response, with increasing resistance increasing between 40 and 70 micrometers (part of the interrupted ZX curve).

At a density level of 90 micrometers, maintained at a minimum, the effect is confirmed. Container B according to the invention has a body that is well resistant to pressure and container C is poorly resistant in this respect. Flavor-less container A is in this case outside the invention, but in the present explanation is sufficiently pressure-resistant.

A second way to make the contained product easier and more complete: a container with an elastic arm (Figs 7 to 10):

The technology for producing this container must begin with a tubular project longer than the body and treating one part by forming that part itself above the melting temperature of these outer layers, rather than between 140 and 220 ° C, in the case of that the outer layers are made of polyethylene, then they are crushed between a press which makes them fold, the folds sticking well together and the shoulder surfaces usually have excellent smoothness.

FIG. 7 shows a container having a shoulder formed in the surrounding folds, showing that the pairs of folds such as 51 and 52 correspond to a wavy appearance to the inner ones

51 or to the outer 52 which are crushed.

In the thermal formation cited above, the folds crush strongly, including those of the barrier layer 20 which is included. One arm 55 which is thinner than the body may be obtained. FIG. 8 shows a container 54 with a screw neck according to the invention, obtained directly by heat molding, an outer set and an annular regulator of the outer set forming between them a cut 55 of the upper end of the clamp. FIG. 9 shows a container 5b obtained also by means of warm molding and shaped with an annular outer crown 57, which is perfectly sealed exterior and excellent tr end of ^k $$ £ 1y ^[e § ^and formed at 5b. The same is put into place by means of a device with the pressure of a ring-shaped matrix of PE heated to 1 ° C, thus treated with a cast in a paste-like state, which is placed above the melting point. Putting the annular crown in place can be achieved by casting, injection molding or ultrasonic bonding. Containers 54 and 56 each have a body of container B, a density of 0.545 mm formed by a heat-molded top and an annular arm 58 which has a density established at the requirements of between 0.5 and 0.4 mm. In the case of container 56 (Fig. 9), the annular crown 57 occupies less than half the width of the ring. the visible arm 58. It can still be crushed laterally to a sufficient shape to improve product disposal. The structure of the container 56 comprising the fusion of the arm 58 with the annular crown 57 (Fig. 10) shows the efficiency of crushing and brazing the folds at the top, such as excellent soldering of the annular crown 57:

- a double fold 59 of the barrier layer 20 shows the end point 40, which avoids the need for flattening

- 15 folds, accompanied by two very thin folds 41,

- a second part 42 of the barrier layer belongs to a double-fold soldered fold containing a double fold 59 of the barrier layer 20,

- on the rights of the end point 40 and the double crease 59 is the crown 57 of the PE as outer layers of the tube 56,

- the soldering time between the folds and between those folds forming the shoulder and the annular crown is excellent. The section shows locally the adhesive layers such as 21, but there is no break in the PE that encloses the described elements;

- the resulting thinning is surprising, it can be adjusted as desired by selecting a temperature for hot forming and by crushing the set.

Industrial application

A flexible plastic body container allows a better preservation of the aroma of the contained product, such as liquid, creamy or pasty. The containers also allow for easy and complete delivery of the product. Especially in the production of cosmetics, pharmaceuticals, hygiene and storage products.

Claims (12)

Patent Claims 1. A container (B, C, 54, 56) for storing and distributing a product, for example, flavored or perfumed, containing water having an upper spreading portion (58, 55) fixed to a multilayer flexible body, the body comprising already an intermediate polymer layer serving as a barrier (20) to oxygen and aromas or essences, the aforementioned layer being sensitive to moisture and having one or more polymer layers (1, 100, 15, on each side of that intermediate layer); 11, and 12, 14, 10) based on polyolefins, all of which are as follows: and cited layers are interconnected in a continuous manner, characterized in that the integrity of the disposed layers on the inside of the cited interlayer having a barrier effect (1, 21, 100, 15, 11, 21) has a total density within between 40 and 150 micrometers as a way to store well the aroma of a product that is or will be in the container. Container according to claim 1, characterized in that the cited density of the layers (1, 21, 100, 15, 11, 12) disposed on said inner part of the intermediate layer is between 55 and 140 micrometers, soon between 65 and 150 micrometers. Container according to any one of claims 1 and 2, characterized in that said polyolefin-based polymer layers consist, on one side, of a low (1) or very low specific gravity or linear polyethylene surface layer low density (100), specific mass reaching between 0.86 and 0.95 g / cm ^? and, on the other hand, the other layers, which are respectively of low specific gravity polyethylene (PE.BD), a specific mass reaching between 0.90 and 0.95 g / cm ³ , or of high specific polyethylene - 17 weight (PE.HD), specific mass between 0.955 and 0.97 g / cm3 (15, 14). A container (B, 54, 56) according to claim 5, characterized in that said layers of polyethylene comprise one or more layers of high specific gravity polyethylene pe.hd (15, 14) with a total density preferably equal to 90 micrometer. 5- Container according to claim 4, characterized in that the quoted sum of the densities of the layers of PE.HD (15, 14) is in the range between 100 and 140 micrometers, the density of the quoted bodies of the containers is in the range of 260 and 580 micrometer. A container according to claim 4, characterized in that the sum of twice the density of the quoted barrier layer (20) and the quoted densities of the pe.hd layers (15, 14) is in the range of 150 to 180 micrometers, the quoted body should be between 260 and 580 micrometers. Container according to any one of claims 5 to 6, characterized in that said polyethylene layers comprise a first layer (15) of pe.hd which is disposed between said surface inner layer (100) and the first intermediate layer layer (11) of PE.BD, it is also located inside the intermediate layer with a barrier effect. Container according to any one of claims 5 to 7, characterized in that said polyethylene layers comprise a second layer (14) of PE.HD which is inserted between an outer layer (10) of PE. BD and one second intermediate layer (12) of pe.bd, the same located at the outside of the intermediate layer with barrier effect (20). 9- A container according to any one of claims 7 or 8, characterized in that the quoted first layers (15) of PE.HD and / or the quoted second layers of PE.HD (14) are in a continuous merger with the quoted layers of pe.bd (100, 11; 12 , 10) of which it (s) is (are) appropriate. Container (B, 54, 56) according to claim 8, according to claim 7, characterized in that the densities of said first and second layers (15, 14) of PE.HD are respectively between 10 and 50 micrometers and between 60 and 140 micrometers. Container (B, 54, 56) according to claim 10, characterized in that said first and second intermediate layers of pe.bd (11, 15) are each individually connected to one side of said intermediate layer with a barrier effect (11). 20) through a bonding layer (21, 22) of EAA or EMA. A container according to any one of claims 1 to 11, characterized in that said intermediate barrier layer (20) of the body is one of the materials of the formed group by: EVOH, PVOH, PA, PA-modified , and has a density between 0,01 and 0,05 mm. Container (54, 56) according to any one of the preceding claims, characterized in that the cited top for distribution (58 and 55) comprises a neck (55) with a diameter smaller than the body and an annular arm ( 58) connecting the neck (55) to the body, this arm having a density in the range of 0.9 times to 1.55 times the density of the body, and in continuation of this structure follows the body cited and surrounding crushed and soldered folds, such as the quoted arm (58) is easily laterally folded. 14. Container (56) according to claim 15, characterized in that the crushed and welded to each other folds of the said arm comprise corrugations which are ⁿ j | yyy ^and as extended (59, 41) of the said intermediate layer with a barrier effect (20) of the body.