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EP0310489A1 - Absorbent pad for packaging - Google Patents

Absorbent pad for packaging Download PDF

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Publication number
EP0310489A1
EP0310489A1 EP88402425A EP88402425A EP0310489A1 EP 0310489 A1 EP0310489 A1 EP 0310489A1 EP 88402425 A EP88402425 A EP 88402425A EP 88402425 A EP88402425 A EP 88402425A EP 0310489 A1 EP0310489 A1 EP 0310489A1
Authority
EP
European Patent Office
Prior art keywords
fibers
absorbent structure
agent
hydroreactive
mattress
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88402425A
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German (de)
French (fr)
Other versions
EP0310489B1 (en
Inventor
Michel Pierre
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaysersberg SA
Original Assignee
Kaysersberg SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaysersberg SA filed Critical Kaysersberg SA
Priority to AT88402425T priority Critical patent/ATE62198T1/en
Publication of EP0310489A1 publication Critical patent/EP0310489A1/en
Application granted granted Critical
Publication of EP0310489B1 publication Critical patent/EP0310489B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/264—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing liquids

Definitions

  • the present invention relates to the field of packaging, and is aimed at the long-term packaging of products, in particular food products, by modification of their surrounding atmosphere by means of an absorbent element containing hydroreactive products.
  • the two methods are sometimes implemented jointly by mixing absorbent materials with active materials or by depositing the latter on an absorbent support by impregnation or coating.
  • Patent GB 496935 describes an oxidizable metallic product or ferrous sulphate mixed or not with other substances, such as citric acid, to slow down the action of microorganisms.
  • Patent application EP 206343 presents a mixture of iron powder and electrolytic agent, in the form of paper.
  • Other patents complete the range of products capable of absorbing oxygen such as sulfites (US 2,825,651), bisulfites (US 3,169,068), or metal oxides (US 3,361,531) resulting from the decarbonation of metallic carbonates, or else ascorbic acid or its salts (French patent 2,394,988).
  • the absorbent agents mentioned are fibers, clays, bentonites, kaolins, active alumina, activated carbon.
  • Patent application JP 80/29975 describes an impregnated material covered with an oxygen absorbing agent and a carbon dioxide generating agent.
  • Patent EP 128795 describes a tray bottom containing, in an absorbent means, not only a material capable of giving off a gas under the effect of an aqueous liquid, but also components of the foodstuff allowing, by aerosol effect, '' inhibit its degradation.
  • the absorbent material is a sheet or a tea bag.
  • the active agent can be a bactericide included in a cellulose sponge as described in patent GB 863095.
  • the invention is aimed at those which become active under the action of a fluid either released by the product which it is desired to preserve, or resulting from the condensation of vapor.
  • the invention proposes to solve the problem which consists in prolonging the action of these means as long as possible. Analysis of the prior art has shown that this problem has not yet been addressed.
  • the powder tends to gather in lumps under the effect of humidity. A part thus loses its accessibility to the liquid and becomes ineffective.
  • an absorbent structure containing at least one water-reactive agent intended to be placed inside a packaging, of foodstuffs in particular, to absorb liquids, exudates or condensates therefrom. in contact with which the agent reacts and releases at least one active element, characterized in that it consists at least of a mattress made up of an essentially fibrous mixture, formed by the aeraulic route, of hydrophilic materials and hydrophobic materials, inside which said hydroreactive agent is distributed.
  • Such a structure has the following advantages: -
  • the distribution of the agent, which is in the form of powder or granules, inside a fiber mat avoids any risk of clumping.
  • the product does not lose its effectiveness.
  • This structure offers the possibility of incorporating a relatively large quantity of powder or granules.
  • the expiry date (DLC) can be extended significantly and reliably because we can guarantee a long-lasting action on the atmosphere confined in the packaging.
  • the mattress is formed by air flow, that is to say that the fibrous materials are transported in an air flow, then deposited on a carpet, with possible premixing of the powders, allows very high production rates. high and thus makes its cost very low. Furthermore, the materials forming the support for the powder can be chosen very inexpensively. - The aeraulic process makes it possible not to use water during training or, if necessary, for the reinforcement of the mattress, which avoids possible degradation, even partial, of the water-reactive agent with water.
  • This structure is preferably covered on each of its faces with a veil or a film, permeable or impermeable as required, so as to control the penetration of liquids inside the mattress.
  • the absorbent complex can be reinforced according to known techniques using hot-melt fiber or powder binders. It is also possible to use aqueous latexes applied on the surface by spraying or in the form of a foam. When the complex is thus consolidated, it is possible to avoid having to coat it on one side of a veil or a film.
  • the mattress containing the hydroreactive materials can be combined with at least one second absorbent mattress consisting for example of bonded fibers, whose wettability is different from the first mattress, and which will form a buffer element between the source of liquids and the structure containing the reagents, so as to increase the delay effect, and to control the distribution and the action of the liquid towards the other mattress.
  • at least one second absorbent mattress consisting for example of bonded fibers, whose wettability is different from the first mattress, and which will form a buffer element between the source of liquids and the structure containing the reagents, so as to increase the delay effect, and to control the distribution and the action of the liquid towards the other mattress.
  • the absorbent mattress containing the hydroreactive consists of at least one hydrophilic material and another clearly less hydrophilic, that is to say hydrophobic compared to the first. In addition, at least one of these components must be fibrous.
  • Hydrophilic component Hydrophobic component .
  • Cellulose fibers Synthetic fibers treated or not Cellulose fibers Latex type binder .
  • Cellulose fibers Hot melt powder binder Hydrophilic powder Synthetic fibers .
  • Treated synthetic fibers Synthetic fibers Treated synthetic fibers Latex and / or powder binder .
  • Treated synthetic fibers Hydrophobic cellulosic fibers .
  • Hydrophilic fibers Less hydrophilic powder
  • Cellulosic fibers include natural fibers, such as cotton or wood, made hydrophilic or hydrophobic depending on the nature of their treatment which determines the amount of residual hydrophobic resin, or regenerated fibers of rayon, viscose, etc. .
  • treated synthetic fibers includes synthetic fibers (PP, PE, PET, etc.) whose surface has been considerably modified to be made more wettable by water (for example PE fibers sold under the brand PULPEX by HERCULES). .
  • Hydrophilic fibers include hydrophilic fibers by nature such as glass fibers or metaphosphates.
  • the hydrophilic powder can be mineral or organic.
  • Mineral powders include clays, vermiculites, glass, etc.
  • Organic powders are of natural origin (guar, alginate, modified celluloses or starches, thickeners, viscosants or hydrogelifiers ...) or synthetic powders (polyethylenoxides, polyvinyl alcohols, polycarboxylates ). These powders are more or less hydrophilic - like fibers - because they can be slow to wet (hydrophobia) and / or capable of gelling water (hydrogelifying powder) to retain it (hydrophilicity) which has the effect of slowing down the diffusion of water in the mattress - desired character - by the introduction of hydrophobic materials, presently classified less "hydrophilic".
  • the hydrophilic component of the mixture can be one of the hydrophilic components mentioned above or else a mixture of two or more of these.
  • a hydrophilic powder in particular a hydrogelifier, to cellulosic fibers.
  • the ratio between hydrophilic and hydrophobic materials must be chosen so as to obtain a wettability of the product compatible with the intended application, that is to say the nature and the quantity of liquids present in the packaging. We will most often try to obtain the lowest possible wettability without making the product completely hydrophobic, that is to say that it cannot absorb liquid.
  • the amount of hydrophobic material can vary from 5 to 50% of the mass of the absorbent structure, excluding the hydroreactive agent.
  • hydrophilic or hydrophobic for which a product is designated.
  • the hydrophilicity of a product depends on its surface energy. It is known that a liquid wets all the better a flat surface that the difference of the surface energies of the liquid and the surface of the solid is small. Thus, water with a surface energy of 72 mJ / m2 wets polyester (43mJ / m2) or cellulose (36 mJ / m2) or polypropylene (29 mJ / m2) well. Water does not wet teflon or PTFE, the surface energy of which is very low (18 mJ / m2).
  • the first surfaces are considered to be hydrophilic while PP, PE or, even more so, PTFE are known to be hydrophobic, because their surface energies are much lower than those of water.
  • a RHODORSIL 6356 silicone binder from RP (25 mJ / m2) is more hydrophobic than a phenolic binder at 42 mJ / m2 or an epoxy adhesive (44.5 mJ / m2) EPIKOTE 828.
  • the surface of the fibers is not flat and their roughness changes the contact angle of the liquid on this surface.
  • MILLER exposed in COLLOIDS AND SURFACES, 6, (1983), 49-61 consisting in measuring the angle of the liquid with the fiber coming into contact with the liquid and the angle of withdrawal when the fiber is removed from the liquid.
  • MILLER has obtained the following values: Angles (in degrees) of contact withdrawal Teflon 118 92 Polypropylene 100 78 Polystyrene (PS) 95 71 PS - Polyacrylonitrite 83 51 Nylon 6 69 25
  • the measurement of the contact angle is decisive for judging the hydrophobicity or hydrophilicity of a material, fiber in particular, because a hydrophobic product can be treated superficially to make it hydrophilic and vice versa.
  • hydroreactive agents, or hydroreactive materials, contained in the absorbent complex are, by definition, sensitive to water, liquid or vapor.
  • hydroreactive compound of the hydroreactive material is not necessarily the active agent of the composition.
  • water can decompose a hydrogenated compound into hydrogen which, in the presence of a catalyst, combines with oxygen to obtain an oxygen-free enclosure.
  • the hydroreactive compound can be the soluble capsule containing active agents.
  • the hydroreactive material is composed of one or more pure or mixed products, mineral or organic products at least partially soluble or capable of combining with water or of reacting or composing.
  • mineral salts NaCl, CaCL2
  • organic salts gluconates, etc.
  • bases Ca (OH) 2, NaOH, etc.
  • acids citric, ascorbic acids
  • soluble materials sugar
  • oxides CaO, MnO
  • peroxides percarbonate 2Na2 CO3, 3H2O2
  • hydrides metals encapsulated or not (Na, Fe ...), carboxymethylcelluloses. ..
  • the water-reactive material consists of two or more components, it is possible to distribute each of the components in a separate fibrous mat or a layer distinct from the mattress which is thus multilayer.
  • the water-reactive material can already be ā€œstabilizedā€, that is to say treated to be less reactive with atmospheric water, which also has the secondary effect of tempering and delaying the reactivity of the material with water.
  • the water-reactive material can be in the form of powder, granules, flakes, laminates, vermicelli or even fibers.
  • the behavior of three products according to the invention is described compared to that of two articles according to the state of the art, by means of three tests.
  • a first test makes it possible to evaluate the total absorption and the instantaneous absorption of the product. Obviously, in order to delay the reaction, a low wettability is sought. However, this remains sufficient so that, in practice, the liquid can be absorbed as it is emitted.
  • the sample product is placed in an Erlen-Meyer bottle which is closed by a stopper pierced with two holes.
  • the first is surmounted by a bulb through which water is introduced in an amount 50% greater than the total absorption of the sample.
  • the second is connected to a water pressure gauge on which the pressure due to gas evolution can be followed.
  • the maximum pressure in water column (CE) and the total reaction time are measured, then the time it takes for the water column to drop to half the maximum value reached is counted; the reaction time is thus defined.
  • a third test is to simulate the wetting of the product placed in the bottom of a container.
  • the container is never strictly horizontal, so that the liquid generally flows on one of the edges of the product.
  • the absorption is carried out by capillarity according to the law of Lucas, it is practically independent of the angle of inclination.
  • the Klemm test makes it possible to follow the rise of the liquid as a function of time on a sample suspended on a balance by measuring the wet height and the quantity of water absorbed.
  • the total absorption is determined at the end of the experiment by immersion of the sample and then vertical drainage.
  • a hydroreactive mixture of powders is prepared from three parts of an equimolar mixture of percarbonate and an organic diacid, and a part of neutral salt serving as an excipient, such as sodium chloride.
  • the percarbonate used is stabilized. In an aqueous medium, it releases oxygen (13%) and carbon dioxide under the action of acid.
  • 6 x 10 cm sachets are made with a nonwoven sold under the brand SERICEL, consisting of a plastic grid laminated with two sheets of cellulose wadding.
  • the same hydroreactive mixture in the same quantity as in Example 1, is introduced into a sachet made by assembling a sheet of cellulose fibers bound by spraying with latex, of grammage 60 g / m2 -product sold under the brand HOMECEL by the Company KAYSERSBERG - and a sheet of SERICEL grammage 60 g / m2.
  • the 6 x 10 cm sachet, 3.5 g, containing 2 g of water-reactive mixture - structure in accordance with the teaching of the state of the art - has an absorption of 9.7 g and a wettability of 88%. (without powder the wettability is 95%).
  • the sachet wets quickly, which has the effect of promoting the hydrolysis of the reagent and goes against the objective. Indeed, it is found according to the second test that the reaction time is shorter (3 min) for a maximum pressure of 28 cm C.E. The reaction time of 45 min is also shorter than in Example 1.
  • the third test confirms that this sachet is more wettable than the previous one, and the effectiveness of the water-reactive mixture is lower.
  • the total absorption here is 7.5 g with a sample of 2.5 g.
  • the absorptions are respectively: 65% after one minute 84% after ten minutes 84% after one hour
  • the absorption of this product is, after one hour, greater than 75% of the capacity.
  • an absorbent complex containing the same hydroreactive material is formed.
  • we defibe pulp of cellulosic fibers product sold under the brand Rayfloc J by ITT
  • synthetic polyethylene pulp fibers sold under the brand SWP by MITSUI
  • 120% of hydroreactive powder of the mixture described in Example 1 is added.
  • the whole is sucked on 18 g / m2 tissue paper, calendered and thermally bonded in an oven at temperature of 30 - 150 Ā° C to allow the fusion of hydrophobic polyethylene thermobonding fibers.
  • the whole is laminated with hotmelt glue, a polyethylene film on one side and a nonwoven on the other side
  • composition of the 530 g / m2 product is: - tissue paper 18 g / m2 - cellulose fibers 200g / m2 - synthetic fibers 10 g / m2 - hydroreactive powder 250g / m2 (47%) - adhesives 6 g / m2 - polyethylene film 28 g / m2 - nonwoven 18 g / m2
  • a 6 x 10 cm, 3.2 g sample absorbs 16.5 g and its wettability is 82%.
  • the instantaneous absorption of a large quantity of liquid is slightly delayed which allows a strong capillary absorption.
  • reaction time of the product according to the invention is considerably increased, 330 minutes, for an unchanged maximum pressure of 30 cm CE.
  • the reaction time is then 485 minutes for this 3.85 g sample, containing 1.85 g of water-reactive material.
  • the absorptions according to the third test are: 51%: after 1 minute 64%: after 10 minutes 64%: after 60 minutes
  • the absorption after one hour is much less than 75% of the capacity.
  • Example 3 The procedure is as in Example 3, but by introducing more polyethylene fibers, 15% instead of 5%, into the fibrous mixture, in order to further modulate the reactivity of the product.
  • composition of the 400 g / m2 product is: - tissue paper 18 g / m2 - cellulose fibers 160 g / m2 - synthetic fibers 24 g / m2 - hydroreactive powder 144 g / m2 (36%) - adhesives 6 g / m2 - polyethylene film 28 g / m2 - nonwoven 18 g / m2
  • the absorption by immersion is 8.1 g for a sample of 2.7 g.
  • the absorptions by capillary rise are respectively: 40% after 1 minute 57% after 10 minutes 57% after 60 minutes
  • the absorption after one hour does not exceed 75% of the capacity. It is lower than that of the product containing only 5% of hydrophobic fibers.
  • Example 4 The procedure is as in Example 4, but the nonwoven covering one side of the product is replaced by a HOMECEL dry paper, already described, of 60 g / m2. It is an absorbent nonwoven whose wettability is higher than that of the lower layer comprising polyethylene fibers, SWP.
  • This example aims to show that one can realize in one or more operations multilayer complexes.
  • Other means exist for depositing fibers or powders locally, in the form of blocks for example, within a fibrous mass.
  • a 7 x 12 cm sample containing approximately 1.3 g of water-reactive materials, reaches the maximum pressure of 10 cm EC in the presence of water in a reaction time of 1 minute.
  • the reaction time is more than 300 minutes.
  • the pressure remains stable between 8 and 9 cm C.E.
  • the third test confirms that this complex is more wettable.
  • the total absorption being 11.8 g (2.8 g sample).
  • the absorptions are respectively: 54% after 1 minute 63% after 10 minutes 66.5% after 60 minutes
  • the absorption after one hour does not exceed 75% of the capacity.
  • thermoplastic fibers such as SWP from MITSUI or PULPEX from HERCULES.
  • hot-melt powders for example of polyester with low melting point of EASTMAN, makes it possible to obtain more flexible products.
  • the hydrophilic material is composed of natural or regenerated fibers or foams, fibers or foam or absorbent nonwoven based on hydrophilic treated synthetic material.
  • the same partially treated material may have the desired characteristics combining hydrophilicity and hydrophobicity.
  • a sheet of fibers is first formed by a dry route, that is to say by a somehowlic route.
  • the powder is then deposited on the surface which is made to penetrate inside the sheet by blowing air, suction through the thickness of the sheet, or finally a combination of the two means.
  • This sheet containing all or part of the powder may be covered with an additional sheet, also formed by air flow, not containing or containing the other part of the hydroreaction powder.
  • a sheet of 300 g / m2 of cellulose fibers was thus produced containing 20% of polyethylene fibers and incorporating a water-reactive powder of the same composition as in Example 1.
  • This tablecloth was thermobonded by passage in the oven.
  • the rate of dissolution of the water-reactant was monitored by measuring the speed of dissolution of the water-reactive after pouring 120 cc of water onto the sample.
  • Three layers of cellulosic fibers containing synthetic SWP fibers are produced by dry process at the rate of 0%, 5% and 15%, and powdered percarbonate.
  • the tablecloths formed are passed for six seconds to the oven at 150 Ā° C.
  • the dissolution time is measured according to a fourth test, that is to say the time taken by a sample, immersed in distilled water, to obtain the balance of the solution of salt dissolved in water, with stirring. It is found that the dissolution times of the peroxide are increased by the presence of the hydrophobic fibers of the products P5 and P15 as well as, as before, the hydration times of the percarbonate.
  • the rate of dissolution of the acid hydroreagent is controlled according to the method of the 4th test, by immersing the sample in distilled water previously brought to pH 8 with sodium hydroxide.
  • Reference C 0.5 g citric acid CO Cellulose + 0.5 g citric acid C5 Cellulose + 5% SWP + 0.5 g citric acid C15 Cellulose + 15% SWP 0.5 g citric acid grammage (g / m2) 265 280 310
  • Test 4 initial pH 8.2 8.2 8.2 8.2 equilibrium pH 2.6 2.6 2.6 2.6 dissolution time (s) pH 3.2 10 23 28 ā‡ 600

Landscapes

  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Packages (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Joints With Sleeves (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)

Abstract

L'invention concerne le domaine de l'emballage et vise le conditionnement de longue durĆ©e de produits alimentaires, en particulier, par modification de leur atmosphĆØre environnante au moyen d'une structure absorbante contenant des produits hydrorĆ©actifs. La structure objet de l'invention absorbe les liquides, exsudats ou condensats, et engendre un Ć©lĆ©ment actif par rĆ©action de l'agent avec le liquide. Elle est caractĆ©risĆ©e en ce qu'elle est constituĆ©e au moins d'un matelas formĆ©, par voie aĆ©raulique, d'un mĆ©lange essentiellement fibreux de matiĆØres hydrophiles et de matiĆØres hydrophobes Ć  l'intĆ©rieur duquel est rĆ©parti ledit agent hydrorĆ©actif.The invention relates to the field of packaging and is aimed at the long-term packaging of food products, in particular by modifying their surrounding atmosphere by means of an absorbent structure containing hydroreactive products. The structure which is the subject of the invention absorbs liquids, exudates or condensates, and generates an active element by reaction of the agent with the liquid. It is characterized in that it consists of at least one mattress formed, by air flow, of an essentially fibrous mixture of hydrophilic materials and hydrophobic materials inside which said hydroreactive agent is distributed.

Description

La prĆ©sente invention concerne le domaine de l'emballage, et vise le conditionnement de longue durĆ©e de produits notamment alimentaires par modification de leur atmosphĆØre environnante au moyen d'un Ć©lĆ©ment absorbant contenant des produits hydrorĆ©actifs.The present invention relates to the field of packaging, and is aimed at the long-term packaging of products, in particular food products, by modification of their surrounding atmosphere by means of an absorbent element containing hydroreactive products.

Les techniques, actuellement connues, de rĆ©alisation de matĆ©riaux perĀ­mettant le contrĆ“le de l'atmosphĆØre confinĆ©e dans un emballage font appel, soit Ć  l'utilisation de fonds absorbants pour sĆ©parer l'eau exsudĆ©e ou condensĆ©e du produit conditionnĆ©, soit Ć  l'utilisation d'agents actifs, tels que des agents dessicants ou bactĆ©riostatiques, en poudre solide dans un sachet.The techniques currently known for producing materials allowing the control of the atmosphere confined in a package call for either the use of absorbent bottoms to separate the exuded or condensed water from the conditioned product, or the use of active agents, such as desiccants or bacteriostats, in solid powder in a sachet.

Les deux mĆ©thodes sont parfois mises en oeuvre conjointement par mĆ©lange des matiĆØres absorbantes aux matiĆØres actives ou par dĆ©pĆ“t de ces derniĆØres sur un support absorbant par imprĆ©gnation ou enduction.The two methods are sometimes implemented jointly by mixing absorbent materials with active materials or by depositing the latter on an absorbent support by impregnation or coating.

En effet, pour la conservation d'un produit, alimentaire ou non, dans un emballage, la premiĆØre condition est d'en sĆ©parer le liquide recueilli. Le plus aisĆ© est la crĆ©ation d'un double fond perforĆ©, comme dĆ©crit dans le brevet britannique 1131848. D'autres barquettes contiennent des feuilles de papier absorbant. Le brevet US 4275811 dĆ©crit un matĆ©riau absorbant revĆŖtu d'une feuille impermĆ©able perforĆ©e pour sĆ©parer le produit alimentaire Ć  conserver de la matiĆØre absorbante mouillĆ©e. Dans la demande de brevet JP 61/058658 ou le brevet US 4615923 le fond absorbant contient des matiĆØres hydrogĆ©lifiantes capables de retenir les liquides aqueux. Pour mieux sĆ©parer le liquide du produit, il est parfois proposĆ© de disposer un double fond intĆ©rieur perforĆ© comme dans la demande de brevet FR 2586653.Indeed, for the conservation of a product, food or not, in a packaging, the first condition is to separate the collected liquid. The easiest is to create a double perforated bottom, as described in British patent 1131848. Other trays contain sheets of absorbent paper. US Pat. No. 4,275,811 describes an absorbent material coated with a perforated impermeable sheet to separate the food product to be preserved from the wet absorbent material. In patent application JP 61/058658 or US patent 4615923 the absorbent bottom contains hydrogelling materials capable of retaining aqueous liquids. To better separate the liquid from the product, it is sometimes proposed to have a double interior perforated bottom as in patent application FR 2586653.

Pour contrĆ“ler l'atmosphĆØre, on utilise diffĆ©rents rĆ©actifs selon l'effect recherchĆ©. Ainsi les emballages contiennent souvent des sachets de silicagel ou de chlorure de calcium pour dĆ©shydrater l'atmosphĆØre, c'est-Ć -dire pour piĆ©ger l'eau vapeur en eau liquide. Souvent, il convient d'absorber l'oxygĆØne contenu dans l'emballage. Le brevet GB 496935 dĆ©crit un produit mĆ©tallique oxydable ou du sulfate ferreux mĆ©langĆ© ou non Ć  d'autres substances, comme l'acide citrique, pour freiner l'action des microorganismes.To control the atmosphere, different reagents are used depending on the desired effect. Thus the packages often contain sachets of silica gel or calcium chloride to dehydrate the atmosphere, that is to say to trap the steam water into liquid water. Often, the oxygen in the package should be absorbed. Patent GB 496935 describes an oxidizable metallic product or ferrous sulphate mixed or not with other substances, such as citric acid, to slow down the action of microorganisms.

La demande de brevet EP 206343 prĆ©sente un mĆ©lange de poudre de fer et d'agent Ć©lectrolytique, sous forme de papier. D'autres brevets complĆØtent l'Ć©ventail des produits susceptibles d'absorber l'oxygĆØne comme les sulfites (US 2825651), les bisulfites (US 3169068), ou les oxydes mĆ©talliques (US 3361531) issus de la dĆ©carbonatation de carboĀ­nates mĆ©talliques, ou encore l'acide ascorbique ou ses sels (brevet franƧais 2394988). Les agents absorbants citĆ©s sont les fibres, les argiles, bentonites, kaolins, l'alumine active, le charbon actif. La demande de brevet JP 80/29975 dĆ©crit un matĆ©riau imprĆ©gnĆ© recouvert d'un agent absorbant l'oxygĆØne et un agent gĆ©nĆ©rateur de gaz carbonique. Parfois, il est utile de gĆ©nĆ©rer de l'oxygĆØne par action de l'eau, comme dans la demande de brevet JP 61/145270 oĆ¹ la poudre est contenue dans un sachet. Le brevet EP 128795 dĆ©crit un fond de barquette contenant, dans un moyen absorbant, non seulement un matĆ©riau susceptible de dĆ©gager un gaz sous l'effet d'un liquide aqueux, mais aussi des composants de la denrĆ©e alimentaire permettant, par effet aĆ©rosol, d'inhiber sa dĆ©graĀ­dation. La matiĆØre absorbante est une feuille ou une infusette.Patent application EP 206343 presents a mixture of iron powder and electrolytic agent, in the form of paper. Other patents complete the range of products capable of absorbing oxygen such as sulfites (US 2,825,651), bisulfites (US 3,169,068), or metal oxides (US 3,361,531) resulting from the decarbonation of metallic carbonates, or else ascorbic acid or its salts (French patent 2,394,988). The absorbent agents mentioned are fibers, clays, bentonites, kaolins, active alumina, activated carbon. Patent application JP 80/29975 describes an impregnated material covered with an oxygen absorbing agent and a carbon dioxide generating agent. Sometimes it is useful to generate oxygen by the action of water, as in patent application JP 61/145270 where the powder is contained in a sachet. Patent EP 128795 describes a tray bottom containing, in an absorbent means, not only a material capable of giving off a gas under the effect of an aqueous liquid, but also components of the foodstuff allowing, by aerosol effect, '' inhibit its degradation. The absorbent material is a sheet or a tea bag.

Pour Ć©viter la dĆ©liquescence des agents actifs par le liquide, la prĆ©Ā­sence d'un matĆ©riau absorbant est nĆ©cessaire mĆŖme dans les sachets contenant ces agents sous forme de poudre ou de granulĆ©s. Pour pouvoir rĆ©utiliser l'agent dessicant, le brevet US 4615823 dĆ©crit une composiĀ­tion oĆ¹ les sels dĆ©liquescents sont maintenus dans un sac grĆ¢ce Ć  des fibres, tandis que les brevets japonais 56/143263 et 61/103523 dĆ©crivent la rĆ©tention du liquide salin dans le sachet grĆ¢ce Ć  des agents gĆ©liĀ­fiants.To avoid the disintegration of the active agents by the liquid, the presence of an absorbent material is necessary even in the sachets containing these agents in the form of powder or granules. To be able to reuse the desiccant, US Pat. No. 4,615,823 describes a composition in which the deliquescent salts are kept in a bag by means of fibers, while the Japanese patents 56/143263 and 61/103523 describe the retention of the saline liquid in the sachet. thanks to gelling agents.

L'agent actif peut ĆŖtre un bactĆ©ricide inclus dans une Ć©ponge de celluĀ­lose comme cela est dĆ©crit dans le brevet GB 863095.The active agent can be a bactericide included in a cellulose sponge as described in patent GB 863095.

Parmi les moyens destinĆ©s Ć  contrĆ“ler l'atmosphĆØre d'un emballage, l'invention vise ceux qui deviennent actifs sous l'action d'un fluide soit libĆ©rĆ© par le produit que l'on veut conserver, soit rĆ©sultant de la condensation de vapeur.Among the means intended to control the atmosphere of a package, the invention is aimed at those which become active under the action of a fluid either released by the product which it is desired to preserve, or resulting from the condensation of vapor.

L'invention se propose de rĆ©soudre le problĆØme qui consiste Ć  prolonger l'action de ces moyens le plus longtemps possible. L'analyse de l'art antĆ©rieur a montrĆ© que ce problĆØme n'avait pas encore Ć©tĆ© abordĆ©.The invention proposes to solve the problem which consists in prolonging the action of these means as long as possible. Analysis of the prior art has shown that this problem has not yet been addressed.

En effet, quand les poudres ou granulĆ©s sont enfermĆ©s dans un sachet, ils rĆ©agissent dĆØs que le liquide a traversĆ© la paroi de ce dernier. La production de gaz ou d'Ć©lĆ©ment actif est de ce fait incontrĆ“lĆ©e.When the powders or granules are enclosed in a sachet, they react as soon as the liquid has passed through the wall of the latter. The production of gas or active element is therefore uncontrolled.

Dans le cas oĆ¹ les liquides sont Ć©mis progressivement, pendant toute la durĆ©e de conservation d'une durĆ©e alimentaire par exemple, il est posĀ­sible de prolonger l'action de ces Ć©lĆ©ments en en disposant une quantitĆ© en excĆØs par rapport Ć  celle du liquide qui doit ĆŖtre recueilli. Mais les produits sont relativement onĆ©reux et cette solution n'est pas Ć©coĀ­nomiquement intĆ©ressante.In the case where liquids are emitted gradually, during the entire shelf life of a food period for example, it is possible to prolong the action of these elements by placing an amount in excess relative to that of the liquid which must to be collected. But the products are relatively expensive and this solution is not economically attractive.

Par ailleurs, dans un sachet, la poudre a tendance Ć  se rassembler en mottes sous l'effet de l'humiditĆ©. Une partie perd ainsi de son acessiĀ­bilitĆ© au liquide et devient inefficace.In addition, in a sachet, the powder tends to gather in lumps under the effect of humidity. A part thus loses its accessibility to the liquid and becomes ineffective.

Enfin, la fabrication et le remplissage des sachets sont des opƩrations coƻteuses. Ce type de support n'est pas rentable Ʃconomiquement au regard de son emploi dans des barquettes de conditionnement de denrƩes alimentaires, par exemple, dont il ne devrait reprƩsenter qu'une faible partie de la valeur.Finally, the manufacture and filling of the sachets are costly operations. This type of support is not economically profitable in view of its use in food packaging trays, for example, of which it should represent only a small part of the value.

Si on prend en considĆ©ration la technique d'enduction sur un support, on se heurte alors au problĆØme de la quantitĆ© trĆØs limitĆ©e de rĆ©actifs qu'il est possible de fixer, par ce moyen, par unitĆ© de surface. Il n'est pas possible, non plus, de contrĆ“ler dans le temps l'effet du produit. On sait par ailleurs que certains hydrorĆ©actifs ne peuvent ĆŖtre appliquĆ©s en solvant aqueux par imprĆ©gnation ou enduction sans ĆŖtre altĆ©rĆ©s.If we take into account the technique of coating on a support, we come up against the problem of the very limited quantity of reagents that it is possible to fix, by this means, per unit of surface. It is also not possible to control the effect of the product over time. It is also known that certain water-reactants cannot be applied as an aqueous solvent by impregnation or coating without being altered.

ConformĆ©ment Ć  l'invention, on remĆ©die Ć  ces inconvĆ©nients en rĆ©alisant une structure absorbante contenant au moins un agent hydrorĆ©actif, desĀ­tinĆ©e Ć  ĆŖtre disposĆ©e Ć  l'intĆ©rieur d'un emballage, de denrĆ©es alimenĀ­taires notamment, pour en absorber les liquides, exsudats ou condensats au contact desquels l'agent rĆ©agit et libĆØre au moins un Ć©lĆ©ment actif, caractĆ©risĆ©e en ce qu'elle consiste au moins en un matelas constituĆ© d'un mĆ©lange essentiellement fibreux, formĆ© par voie aĆ©raulique, de matiĆØres hydrophiles et de matiĆØres hydrophobes, Ć  l'intĆ©rieur duquel ledit agent hydrorĆ©actif est rĆ©parti.In accordance with the invention, these drawbacks are remedied by producing an absorbent structure containing at least one water-reactive agent, intended to be placed inside a packaging, of foodstuffs in particular, to absorb liquids, exudates or condensates therefrom. in contact with which the agent reacts and releases at least one active element, characterized in that it consists at least of a mattress made up of an essentially fibrous mixture, formed by the aeraulic route, of hydrophilic materials and hydrophobic materials, inside which said hydroreactive agent is distributed.

Une telle structure prƩsente les avantages suivants :

- La rĆ©partition de l'agent, qui est sous forme de poudre ou de graĀ­nulĆ©s, Ć  l'intĆ©rieur d'un matelas de fibres Ć©vite tout risque d'agglomĆ©ration en mottes. Le produit ne perd ainsi pas de son efficacitĆ©. Cette structure offre la possibilitĆ© d'incorporer une quantitĆ© relativement importante de poudre ou granulĆ©s.

- Il est possible, par un choix convenable des quantitĆ©s de matiĆØres hydrophiles et hydrophobes, d'ajuster la vitesse de mouillage de la structure, et ainsi de contrĆ“ler la durĆ©e de rĆ©action. Dans le cas de conservation des denrĆ©es alimentaires, la date limite de conserĀ­vation (DLC) pourra ĆŖtre reculĆ©e de faƧon significative et fiable car on pourra garantir une action de longue durĆ©e sur l'atmosphĆØre confinĆ©e dans l'emballage.

- Le fait que le matelas soit formĆ© par voie aĆ©raulique, c'est-Ć -dire que les matiĆØres fibreuses soient transportĆ©es dans un flux d'air, puis dĆ©posĆ©es sur un tapis, avec prĆ©mĆ©lange Ć©ventuel des poudres, permet des cadences de fabrication trĆØs Ć©levĆ©es et rend de la sorte son coĆ»t trĆØs faible. Par ailleurs les matiĆØres formant le support de la poudre peuvent ĆŖtre choisies trĆØs bon marchĆ©.

- Le procĆ©dĆ© par voie aĆ©raulique permet de ne pas employer d'eau lors de la formation ou si besoin est, pour le renforcement du matelas, ce qui Ć©vite une Ć©ventuelle dĆ©gradation mĆŖme partielle de l'hydroĀ­rĆ©actif par l'eau.Such a structure has the following advantages:

- The distribution of the agent, which is in the form of powder or granules, inside a fiber mat avoids any risk of clumping. The product does not lose its effectiveness. This structure offers the possibility of incorporating a relatively large quantity of powder or granules.

- It is possible, by a suitable choice of the quantities of hydrophilic and hydrophobic materials, to adjust the wetting speed of the structure, and thus to control the reaction time. In the case of food preservation, the expiry date (DLC) can be extended significantly and reliably because we can guarantee a long-lasting action on the atmosphere confined in the packaging.

- The fact that the mattress is formed by air flow, that is to say that the fibrous materials are transported in an air flow, then deposited on a carpet, with possible premixing of the powders, allows very high production rates. high and thus makes its cost very low. Furthermore, the materials forming the support for the powder can be chosen very inexpensively.

- The aeraulic process makes it possible not to use water during training or, if necessary, for the reinforcement of the mattress, which avoids possible degradation, even partial, of the water-reactive agent with water.

Cette structure est recouverte de prĆ©fĆ©rence sur chacune de ses faces d'un voile ou d'une pellicule, permĆ©able ou impermĆ©able selon les besoins, de maniĆØre Ć  commander la pĆ©nĆ©tration des liquides Ć  l'intĆ©Ā­rieur du matelas.This structure is preferably covered on each of its faces with a veil or a film, permeable or impermeable as required, so as to control the penetration of liquids inside the mattress.

Selon une forme prĆ©fĆ©rĆ©e de l'invention, le complexe absorbant peut ĆŖtre renforcĆ© selon les techniques connues mettant en oeuvre des liants thermofusibles en fibre ou en poudre. On peut Ć©galement utiliser des latex aqueux appliquĆ©s en surface par pulvĆ©risation ou sous forme de mousse. Lorsque le complexe est ainsi consolidĆ©, on peut Ć©viter d'avoir Ć  le revĆŖtir sur une face d'un voile ou d'une pellicule.According to a preferred form of the invention, the absorbent complex can be reinforced according to known techniques using hot-melt fiber or powder binders. It is also possible to use aqueous latexes applied on the surface by spraying or in the form of a foam. When the complex is thus consolidated, it is possible to avoid having to coat it on one side of a veil or a film.

Selon une autre forme avantageuse de l'invention, le matelas contenant les matiĆØres hydrorĆ©actives peut ĆŖtre combinĆ© Ć  au moins un deuxiĆØme matelas absorbant constituĆ© par exemple de fibres liĆ©es, dont la mouilĀ­labilitĆ© est diffĆ©rente du premier matelas, et qui va former un Ć©lĆ©ment tampon entre la source de liquides et la structure contenant les rĆ©acĀ­tifs, de maniĆØre Ć  augmenter l'effet retard, et Ć  contrĆ“ler la distriĀ­bution et l'action du liquide vers l'autre matelas.According to another advantageous form of the invention, the mattress containing the hydroreactive materials can be combined with at least one second absorbent mattress consisting for example of bonded fibers, whose wettability is different from the first mattress, and which will form a buffer element between the source of liquids and the structure containing the reagents, so as to increase the delay effect, and to control the distribution and the action of the liquid towards the other mattress.

Le matelas absorbant contenant l'hydrorĆ©actif est constituĆ© d'au moins une matiĆØre hydrophile et d'une autre nettement moins hydrophile, c'est-Ć -dire hydrophobe par rapport Ć  la premiĆØre. En outre un de ces composants au moins doit ĆŖtre fibreux.The absorbent mattress containing the hydroreactive consists of at least one hydrophilic material and another clearly less hydrophilic, that is to say hydrophobic compared to the first. In addition, at least one of these components must be fibrous.

On peut choisir parmi les mƩlanges suivants : Composant hydrophile Composant hydrophobe . Fibres cellulosiques Fibres synthƩtiques traitƩes ou non . Fibres cellulosiques Liant du type latex . Fibres cellulosiques Liant en poudre thermofusible . Poudre hydrophile Fibres synthƩtiques . Fibres synthƩtiques traitƩes Fibres synthƩtiques . Fibres synthƩtiques traitƩes Liant latex et/ou en poudre . Fibres synthƩtiques traitƩes Fibres cellulosiques hydrophobes . Fibres hydrophiles Poudre moins hydrophile You can choose from the following mixes: Hydrophilic component Hydrophobic component . Cellulose fibers Synthetic fibers treated or not . Cellulose fibers Latex type binder . Cellulose fibers Hot melt powder binder . Hydrophilic powder Synthetic fibers . Treated synthetic fibers Synthetic fibers . Treated synthetic fibers Latex and / or powder binder . Treated synthetic fibers Hydrophobic cellulosic fibers . Hydrophilic fibers Less hydrophilic powder

Les fibres cellulosiques comprennent les fibres naturelles, telles que celles de coton ou du bois, rendues hydrophiles ou hydrophobe en fonction de la nature de leur traitement qui dƩtermine la quantitƩ de rƩsine rƩsiduelle hydrophobe, ou les fibres rƩgƩnƩrƩes de rayonne, viscose, etc...Cellulosic fibers include natural fibers, such as cotton or wood, made hydrophilic or hydrophobic depending on the nature of their treatment which determines the amount of residual hydrophobic resin, or regenerated fibers of rayon, viscose, etc. .

Par fibres synthĆ©tiques traitĆ©es, on comprend les fibres synthĆ©tiques (PP, PE, PET, ...) dont la surface a Ć©tĆ© considĆ©rablement modifiĆ©e pour ĆŖtre rendues plus mouillables par l'eau (par exemple fibres PE vendues sous la marque PULPEX par HERCULES).The term ā€œtreated synthetic fibersā€ includes synthetic fibers (PP, PE, PET, etc.) whose surface has been considerably modified to be made more wettable by water (for example PE fibers sold under the brand PULPEX by HERCULES). .

Par fibres hydrophiles on comprend des fibres hydrophiles par nature telles que fibres de verre ou mƩtaphosphates.Hydrophilic fibers include hydrophilic fibers by nature such as glass fibers or metaphosphates.

La poudre hydrophile peut ĆŖtre minĆ©rale ou organique. Les poudres minĆ©Ā­rales comprennent les argiles, vermiculites, verre, etc... Les poudres organiques sont d'origine naturelle (guar, alginate, celluloses ou amidons modifiĆ©s, produits Ć©paississants, viscosants ou hydrogĆ©liĀ­fiants...) ou synthĆ©tiques (polyĆ©thylinĆ©oxydes, polyvinylalcools, polyĀ­carboxylates...). Ces poudres sont plus ou moins hydrophiles - comme les fibres - car elles peuvent ĆŖtre lentes Ć  se mouiller (hydrophobie) et/ou capables de gĆ©lifier l'eau (poudre hydrogĆ©lifiante) pour la retenir (hydrophilie) ce qui a cependant pour effet de ralentir la diffusion de l'eau dans le matelas - caractĆØre recherchĆ© - par l'introduction des matiĆØres hydrophobes, prĆ©sentement classĆ©es moins "hydrophiles".The hydrophilic powder can be mineral or organic. Mineral powders include clays, vermiculites, glass, etc. Organic powders are of natural origin (guar, alginate, modified celluloses or starches, thickeners, viscosants or hydrogelifiers ...) or synthetic powders (polyethylenoxides, polyvinyl alcohols, polycarboxylates ...). These powders are more or less hydrophilic - like fibers - because they can be slow to wet (hydrophobia) and / or capable of gelling water (hydrogelifying powder) to retain it (hydrophilicity) which has the effect of slowing down the diffusion of water in the mattress - desired character - by the introduction of hydrophobic materials, presently classified less "hydrophilic".

Enfin le composant hydrophile du mĆ©lange peut ĆŖtre l'un des composants hydrophiles mentionnĆ©s ci-dessus ou bien un mĆ©lange de deux ou plusieurs de ceux-ci. Par exemple on pourra ajouter une poudre hydrophile, notamĀ­ment un hydrogĆ©lifiant, Ć  des fibres cellulosiques.Finally, the hydrophilic component of the mixture can be one of the hydrophilic components mentioned above or else a mixture of two or more of these. For example, it is possible to add a hydrophilic powder, in particular a hydrogelifier, to cellulosic fibers.

Le rapport entre les matiĆØres hydrophiles et hydrophobes devra ĆŖtre choisi de faƧon Ć  obtenir une mouillabilitĆ© du produit compatible avec l'application envisagĆ©e, c'est-Ć -dire la nature et la quantitĆ© des liquides prĆ©sents dans l'emballage. On cherchera le plus souvent Ć  obtenir la mouillabilitĆ© la plus faible possible sans rendre le produit totalement hydrophobe, c'est-Ć -dire qu'il ne puisse pas absorber de liquide.The ratio between hydrophilic and hydrophobic materials must be chosen so as to obtain a wettability of the product compatible with the intended application, that is to say the nature and the quantity of liquids present in the packaging. We will most often try to obtain the lowest possible wettability without making the product completely hydrophobic, that is to say that it cannot absorb liquid.

Ainsi, la quantitĆ© de matiĆØre hydrophobe peut varier de 5 Ć  50 % de la masse de la structure absorbante, hors agent hydrorĆ©actif.Thus, the amount of hydrophobic material can vary from 5 to 50% of the mass of the absorbent structure, excluding the hydroreactive agent.

Il importe de dƩfinir les termes hydrophile ou hydrophobe dont on dƩsigne un produit.It is important to define the terms hydrophilic or hydrophobic for which a product is designated.

L'hydrophilie d'un produit dĆ©pend de son Ć©nergie superficielle. On sait qu'un liquide mouille d'autant mieux une surface plane que la diffĆ©rence des Ć©nergies superficielles du liquide et de la surface du solide est faible. Ainsi, l'eau dont l'Ć©nergie superficielle est de 72 mJ/mĀ² mouille bien le polyester (43mJ/mĀ²) ou la cellulose (36 mJ/mĀ²) ou le polypropylĆØne (29 mJ/mĀ²). L'eau ne mouille pas le teflon ou PTFE dont l'Ć©nergie superficielle est trĆØs faible (18 mJ/mĀ²).The hydrophilicity of a product depends on its surface energy. It is known that a liquid wets all the better a flat surface that the difference of the surface energies of the liquid and the surface of the solid is small. Thus, water with a surface energy of 72 mJ / mĀ² wets polyester (43mJ / mĀ²) or cellulose (36 mJ / mĀ²) or polypropylene (29 mJ / mĀ²) well. Water does not wet teflon or PTFE, the surface energy of which is very low (18 mJ / mĀ²).

Les premiĆØres surfaces sont considĆ©rĆ©es comme Ć©tant hydrophiles alors que le PP, PE ou Ć  plus forte raison le PTFE sont connues pour ĆŖtre hydrophobes, car leurs Ć©nergies superficielles sont nettement infĆ©Ā­rieures Ć  celles de l'eau.The first surfaces are considered to be hydrophilic while PP, PE or, even more so, PTFE are known to be hydrophobic, because their surface energies are much lower than those of water.

Par ailleurs, un liant au silicone RHODORSIL 6356 de RP (25 mJ/mĀ²) est plus hydrophobe qu'un liant phĆ©nolique Ć  42 mJ/mĀ² ou une colle Ć©poxy (44,5 mJ/mĀ²) EPIKOTE 828.In addition, a RHODORSIL 6356 silicone binder from RP (25 mJ / mĀ²) is more hydrophobic than a phenolic binder at 42 mJ / mĀ² or an epoxy adhesive (44.5 mJ / mĀ²) EPIKOTE 828.

Malheureusement, la surface des fibres n'est pas plane et leur rugositƩ modifie l'angle de contact du liquide sur cette surface.Unfortunately, the surface of the fibers is not flat and their roughness changes the contact angle of the liquid on this surface.

Pour caractĆ©riser la mouillabilitĆ© d'une fibre il convient de mesurer son angle de contact avec l'eau par exemple d'aprĆØs la mĆ©thode de B. MILLER exposĆ©e dans COLLOIDS AND SURFACES, 6, (1983), 49-61 consisĀ­tant Ć  mesurer l'angle du liquide avec la fibre entrant en contact avec le liquide et l'angle de retrait lorsque l'on retire la fibre du liquide. Pour des fibres rondes, MILLER a obtenu les valeurs suivantes : Angles (en degrĆ©s) de contact de retrait TĆ©flon 118 92 PolypropylĆØne 100 78 PolystyrĆØne (PS) 95 71 PS - Polyacrylonitrite 83 51 Nylon 6 69 25 To characterize the wettability of a fiber, it is necessary to measure its contact angle with water for example according to the method of B. MILLER exposed in COLLOIDS AND SURFACES, 6, (1983), 49-61 consisting in measuring the angle of the liquid with the fiber coming into contact with the liquid and the angle of withdrawal when the fiber is removed from the liquid. For round fibers, MILLER has obtained the following values: Angles (in degrees) of contact withdrawal Teflon 118 92 Polypropylene 100 78 Polystyrene (PS) 95 71 PS - Polyacrylonitrite 83 51 Nylon 6 69 25

Ainsi cette mĆ©thode permet d'Ć©valuer le degrĆ© de mouillabilitĆ©. Lorsque les angles sont supĆ©rieurs Ć  90Ā°, il n'y a pas mouillage de la fibre par l'eau. Elle est complĆØtement hydrophobe. Au contraire, une fibre de cellulose kraft blanchie s'avĆØrerait complĆØtement hydrophile avec des angles de contact et de retrait trĆØs faibles. Il rĆ©sulte de ce qui prĆ©cĆØde que les produits dĆ©signĆ©s par hydrophiles et hydrophobes (dans la prĆ©sente invention) sont des produits dont les angles de contact avec l'eau sont notablement diffĆ©rents. La diffĆ©rence des angles devra ĆŖtre supĆ©rieure Ć  20 degrĆ©s sachant que les fibres dites hydrophiles auront les angles de contact et de retrait les plus faibles, et infĆ©rieurs Ć  90Ā°, pour mĆ©riter l'appellation hydrophile.Thus this method makes it possible to evaluate the degree of wettability. When the angles are greater than 90 Ā°, there is no wetting of the fiber by water. It is completely hydrophobic. On the contrary, a bleached kraft cellulose fiber would prove to be completely hydrophilic with very small contact and withdrawal angles. It follows from the above that the products designated by hydrophilic and hydrophobic (in the present invention) are products whose contact angles with water are significantly different. The difference in angles must be greater than 20 degrees, knowing that the so-called hydrophilic fibers will have the lowest contact and withdrawal angles, and less than 90 Ā°, to merit the hydrophilic designation.

La mesure de l'angle de contact est dĆ©terminante pour juger de l'hydroĀ­phobie ou de l'hydrophilie d'une matiĆØre, fibre notamment, car un produit hydrophobe peut ĆŖtre traitĆ© superficiellement pour le rendre hydrophile et inversement.The measurement of the contact angle is decisive for judging the hydrophobicity or hydrophilicity of a material, fiber in particular, because a hydrophobic product can be treated superficially to make it hydrophilic and vice versa.

Les agents hydrorĆ©actifs, ou matiĆØres hydrorĆ©actives, contenus dans le complexe absorbant sont, par dĆ©finition, sensibles Ć  l'eau, liquide ou vapeur.The hydroreactive agents, or hydroreactive materials, contained in the absorbent complex are, by definition, sensitive to water, liquid or vapor.

Cette rĆ©activitĆ© au sens physico-chimique se traduit par exemple par l'hydratation de la matiĆØre, sa dissolution ou sa dĆ©composition en prĆ©sence de liquide aqueux. Le composĆ© hydrorĆ©actif de la matiĆØre hydroĀ­rĆ©active n'est pas forcĆ©ment l'agent actif de la composition.This reactivity in the physico-chemical sense results, for example, in the hydration of the material, its dissolution or its decomposition in the presence of aqueous liquid. The hydroreactive compound of the hydroreactive material is not necessarily the active agent of the composition.

Ainsi, l'eau peut dĆ©composer un composĆ© hydrogĆ©nĆ© en hydrogĆØne qui, en prĆ©sence d'un catalyseur, se combine Ć  l'oxygĆØne pour obtenir une enceinte sans oxygĆØne. (brevet US 3419400). Le composĆ© hydrorĆ©actif peut ĆŖtre la capsule soluble contenant des agents actifs.Thus, water can decompose a hydrogenated compound into hydrogen which, in the presence of a catalyst, combines with oxygen to obtain an oxygen-free enclosure. (US patent 3419400). The hydroreactive compound can be the soluble capsule containing active agents.

La matiĆØre hydrorĆ©active est composĆ©e d'un ou de plusieurs produits purs ou en mĆ©lange, de produits minĆ©raux ou organiques au moins partiellement solubles ou capable de se combiner avec l'eau ou de rĆ©agir ou de se composer. Ce sont par exemple les sels minĆ©raux (NaCl, CaCLā‚‚), les sels organiques (gluconates...), des bases (Ca(OH)ā‚‚, NaOH..) ou des acides (acides citriques, ascorbiques), des matiĆØres solubles (sucre), des oxydes (CaO, MnO), des peroxydes (percarbonate 2Naā‚‚ COā‚ƒ, 3Hā‚‚Oā‚‚), des hydrures, des mĆ©taux encapsulĆ©s ou non (Na, Fe...), des carboxymĆ©thylĀ­celluloses. ..The hydroreactive material is composed of one or more pure or mixed products, mineral or organic products at least partially soluble or capable of combining with water or of reacting or composing. These are, for example, mineral salts (NaCl, CaCLā‚‚), organic salts (gluconates, etc.), bases (Ca (OH) ā‚‚, NaOH, etc.) or acids (citric, ascorbic acids), soluble materials ( sugar), oxides (CaO, MnO), peroxides (percarbonate 2Naā‚‚ COā‚ƒ, 3Hā‚‚Oā‚‚), hydrides, metals encapsulated or not (Na, Fe ...), carboxymethylcelluloses. ..

Quand la matiĆØre hydrorĆ©active est constituĆ©e de deux composants, ou plus, il est possible de rĆ©partir chacun des composants dans un matelas fibreux distinct ou une couche distincte du matelas qui est ainsi mulĀ­ticouches.When the water-reactive material consists of two or more components, it is possible to distribute each of the components in a separate fibrous mat or a layer distinct from the mattress which is thus multilayer.

La matiĆØre hydrorĆ©active peut dĆ©jĆ  ĆŖtre "stabilisĆ©e" c'est-Ć -dire traitĆ©e pour ĆŖtre moins rĆ©active avec l'eau atmosphĆ©rique, ce qui a Ć©galement pour effet secondaire de tempĆ©rer et de temporiser la rĆ©actiĀ­vitĆ© de la matiĆØre avec l'eau.The water-reactive material can already be "stabilized", that is to say treated to be less reactive with atmospheric water, which also has the secondary effect of tempering and delaying the reactivity of the material with water.

La matiĆØre hydrorĆ©active peut se prĆ©senter sous forme de poudre, de granulĆ©s, de paillettes, de laminĆ©s, de vermicelles ou mĆŖme de fibres. A titre d'exemple, on dĆ©crit le comportement de trois produits selon l'invention comparĆ© Ć  celui de deux articles selon l'Ć©tat de la techniĀ­que, par le moyen de trois tests.The water-reactive material can be in the form of powder, granules, flakes, laminates, vermicelli or even fibers. By way of example, the behavior of three products according to the invention is described compared to that of two articles according to the state of the art, by means of three tests.

Un premier test permet d'Ć©valuer l'absorption totale et l'absorption instantanĆ©e du produit. Bien Ć©videmment on recherche, pour temporiser la rĆ©action, une mouillabilitĆ© faible. Mais celle-ci reste suffisante pour que, dans la pratique, le liquide puisse ĆŖtre absorbĆ© au fur et Ć  mesure de son Ć©mission.A first test makes it possible to evaluate the total absorption and the instantaneous absorption of the product. Obviously, in order to delay the reaction, a low wettability is sought. However, this remains sufficient so that, in practice, the liquid can be absorbed as it is emitted.

Pour ce test on dĆ©pose un Ć©chantillon de 6 x 10 cm sur un plan horizonĀ­tal. On l'inonde d'une certaine quantitĆ© d'eau. Puis on bascule le plan support Ć  30 degrĆ©s tout en rĆ©cupĆ©rant le liquide en excĆØs qui s'Ć©coule. Par diffĆ©rence, on calcule l'absorption totale de l'Ć©chantillon.For this test, a 6 x 10 cm sample is placed on a horizontal plane. It is flooded with a certain amount of water. Then we tilt the support plane to 30 degrees while recovering the excess liquid flowing. By difference, the total absorption of the sample is calculated.

Ensuite, on place un autre Ć©chantillon identique au premier sur le plan inclinĆ© Ć  30 degrĆ©s. A l'aide d'une burette, on verse instantanĆ©ment un quantitĆ© d'eau 50 % supĆ©rieure Ć  ce que le produit peut absorber Ć  saĀ­turation, et on en recueille l'excĆ©dent. Par diffĆ©rence on calcule l'absorption instantanĆ©e qui peut ĆŖtre exprimĆ©e en pourcentage de l'abĀ­sorption totale et appelĆ©e mouillabilitĆ©.Then, place another sample identical to the first on the plane inclined at 30 degrees. Using a burette, instantly pour 50% more water than the product can absorb at saturation, and collect the excess. By difference we calculate the instantaneous absorption which can be expressed as a percentage of the total absorption and called wettability.

Pour Ć©valuer la rĆ©activitĆ© totale du produit, on procĆØde selon le second test suivant. On place le produit Ć©chantillon dans un flacon Erlen-Meyer que l'on ferme par un bouchon percĆ© de deux trous. Le premier est surĀ­montĆ© d'une ampoule par laquelle on introduit de l'eau en quantitĆ© 50 % supĆ©rieure Ć  l'absorption totale de l'Ć©chantillon. Le second est reliĆ© Ć  un manomĆØtre Ć  eau sur lequel on peut suivre la pression due au dĆ©gageĀ­ment gazeux. On mesure la pression maximale en colonne d'eau (C.E.) et le temps total de rĆ©action, puis on compte le temps que met la colonne d'eau pour redescendre Ć  la moitiĆ© de la valeur maximale atteinte ; on dĆ©finit ainsi la durĆ©e de rĆ©action.To assess the total reactivity of the product, we proceed according to the following second test. The sample product is placed in an Erlen-Meyer bottle which is closed by a stopper pierced with two holes. The first is surmounted by a bulb through which water is introduced in an amount 50% greater than the total absorption of the sample. The second is connected to a water pressure gauge on which the pressure due to gas evolution can be followed. The maximum pressure in water column (CE) and the total reaction time are measured, then the time it takes for the water column to drop to half the maximum value reached is counted; the reaction time is thus defined.

Un troisiĆØme test a pour objet de simuler le mouillage du produit placĆ© dans le fond d'un conteneur. Le conteneur n'est jamais rigoureusement Ć  l'horizontale, si bien que le liquide s'Ć©coule gĆ©nĆ©ralement sur un des bords du produit. L'absorption s'effectue par capillaritĆ© selon la loi de Lucas, elle est pratiquement indĆ©pendante de l'angle d'inclinaison. Le test de Klemm permet de suivre sur un Ć©chantillon suspendu Ć  une balance la montĆ©e du liquide en fonction du temps en mesurant la hauteur mouillĆ©e et la quantitĆ© d'eau absorbĆ©e.The purpose of a third test is to simulate the wetting of the product placed in the bottom of a container. The container is never strictly horizontal, so that the liquid generally flows on one of the edges of the product. The absorption is carried out by capillarity according to the law of Lucas, it is practically independent of the angle of inclination. The Klemm test makes it possible to follow the rise of the liquid as a function of time on a sample suspended on a balance by measuring the wet height and the quantity of water absorbed.

On dƩtermine en fin d'expƩrience l'absorption totale par immersion de l'Ʃchantillon puis Ʃgouttage Ơ la verticale.The total absorption is determined at the end of the experiment by immersion of the sample and then vertical drainage.

Nous pouvons ainsi exprimer l'absorption Ć  chaque instant en pourcentage de l'absorption totale par immersion - Ć©gouttage.We can thus express the absorption at each instant as a percentage of the total absorption by immersion - drainage.

EXEMPLE 1EXAMPLE 1

On prĆ©pare un mĆ©lange hydrorĆ©actif de poudres Ć  partir de trois parties d'un mĆ©lange Ć©quimolaire de percarbonate et d'un diacide organique, et d'une partie de sel neutre servant d'excipient, tel que du chlorure de sodium. Le percarbonate utilisĆ© est stabilisĆ©. En milieu aqueux, il libĆØre de l'oxygĆØne (13 %) et du gaz carbonique sous l'action de l'acide.A hydroreactive mixture of powders is prepared from three parts of an equimolar mixture of percarbonate and an organic diacid, and a part of neutral salt serving as an excipient, such as sodium chloride. The percarbonate used is stabilized. In an aqueous medium, it releases oxygen (13%) and carbon dioxide under the action of acid.

On confectionne des sachets de 6 x 10 cm avec un non-tissƩ vendu sous la marque SERICEL, constituƩ d'une grille plastique contrecollƩe de deux feuilles d'ouate de cellulose.6 x 10 cm sachets are made with a nonwoven sold under the brand SERICEL, consisting of a plastic grid laminated with two sheets of cellulose wadding.

Pour le premier test, on place 0,72 g dans un premier sachet et 2 g dans un deuxiĆØme. On constate que dans les deux cas l'absorption totale est de 5,7 g et l'absorption instantanĆ©e de 88 %.For the first test, 0.72 g is placed in a first sachet and 2 g in a second. It can be seen that in both cases the total absorption is 5.7 g and the instantaneous absorption 88%.

Pour le 2ĆØme test, on place Ć  nouveau 2 g dans un sachet. On observe que la pression s'Ć©lĆØve rapidement et atteint son maximum de 33 cm de coĀ­lonne d'eau en un temps de rĆ©action de 2 minutes. On peut conclure que le dĆ©gagement gazeux est instantanĆ©ment dĆ©clenchĆ© par la prĆ©sence d'eau, sans effet retard. La pression diminue ensuite par dissolution des gaz. La durĆ©e de rĆ©action est comptĆ©e Ć  60 minutes.For the 2nd test, 2 g are again placed in a sachet. It is observed that the pressure rises rapidly and reaches its maximum of 33 cm of water column in a reaction time of 2 minutes. We can conclude that the gas evolution is instantly triggered by the presence of water, without delay effect. The pressure then decreases by dissolution of the gases. The reaction time is counted at 60 minutes.

Par comparaison, 2 g de poudre hydrorĆ©active hydrolysĆ©e par 120 ml d'eau provoquent une augmentation de pression de 38 cm C.E. en un temps de rĆ©action de 5 minutes. La durĆ©e de rĆ©action de la poudre seule est de 35 mn environ. Cet exemple ainsi que l'exemple 2, montrent que le temps de rĆ©action reste inchangĆ© et que la durĆ©e de rĆ©action est moins que doublĆ©e lorsque la poudre est accompagnĆ©e de matiĆØres absorbantes selon l'Ć©tant de la technique.By comparison, 2 g of hydroreactive powder hydrolyzed with 120 ml of water cause a pressure increase of 38 cm C.E. in a reaction time of 5 minutes. The reaction time of the powder alone is approximately 35 minutes. This example, as well as example 2, shows that the reaction time remains unchanged and that the reaction time is less than doubled when the powder is accompanied by absorbent materials depending on the state of the art.

EXEMPLE 2EXAMPLE 2

Le mĆŖme mĆ©lange hydrorĆ©actif, en mĆŖme quantitĆ© que dans l'exemple 1, est introduit dans un sachet confectionnĆ© en assemblant une nappe de fibres cellulosiques liĆ©es par pulvĆ©risation de latex, de grammage 60 g/mĀ² -Ā­produit vendu sous la marque HOMECEL par la SociĆ©tĆ© KAYSERSBERG - et une feuille de SERICEL de grammage 60 g/mĀ².The same hydroreactive mixture, in the same quantity as in Example 1, is introduced into a sachet made by assembling a sheet of cellulose fibers bound by spraying with latex, of grammage 60 g / mĀ² -product sold under the brand HOMECEL by the Company KAYSERSBERG - and a sheet of SERICEL grammage 60 g / mĀ².

Le sachet 6 x 10 cm, de 3, 5 g, contenant 2 g de mĆ©lange hydrorĆ©actif -Ā­structure conforme Ć  l'enseignement de l'Ć©tat de la technique - prĆ©sente une absorption de 9,7 g et une mouillabilitĆ© de 88 %. (sans poudre la mouillabilitĆ© est de 95 %).The 6 x 10 cm sachet, 3.5 g, containing 2 g of water-reactive mixture - structure in accordance with the teaching of the state of the art - has an absorption of 9.7 g and a wettability of 88%. (without powder the wettability is 95%).

Le sachet se mouille rapidement, ce qui a pour effet de favoriser l'hyĀ­drolyse du rĆ©actif et va Ć  l'encontre de l'objectif. En effet, on consĀ­tate selon le deuxiĆØme test que le temps de rĆ©action est plus court (3 mn) pour une pression maximale de 28 cm C.E. La durĆ©e de rĆ©action de 45 mn est Ć©galement plus faible qu'Ć  l'exemple 1.The sachet wets quickly, which has the effect of promoting the hydrolysis of the reagent and goes against the objective. Indeed, it is found according to the second test that the reaction time is shorter (3 min) for a maximum pressure of 28 cm C.E. The reaction time of 45 min is also shorter than in Example 1.

Le troisiĆØme test confirme que ce sachet est plus mouillable que le prĆ©cĆ©dent, et l'efficacitĆ© du mĆ©lange hydrorĆ©actif plus faible. L'abĀ­sorption totale est ici de 7,5 g avec un Ć©chantillon de 2,5 g. Les absorĀ­ptions sont respectivement de :

65 % au bout d'une minute
84 % au bout de dix minutes
84 % au bout d'une heureThe third test confirms that this sachet is more wettable than the previous one, and the effectiveness of the water-reactive mixture is lower. The total absorption here is 7.5 g with a sample of 2.5 g. The absorptions are respectively:

65% after one minute
84% after ten minutes
84% after one hour

L'absorption de ce produit est, au bout d'une heure, supƩrieure Ơ 75 % de la capacitƩ.The absorption of this product is, after one hour, greater than 75% of the capacity.

EXEMPLE 3EXAMPLE 3

On constitue, conformĆ©ment Ć  l'invention, un complexe absorbant conĀ­tenant la mĆŖme matiĆØre hydrorĆ©active . Pour cela, on dĆ©fibre de la pĆ¢te de fibres cellulosiques (produit vendu sous la marque Rayfloc J par ITT) et de la pĆ¢te synthĆ©tique de polyĆ©thylĆØne (fibres vendues sous la marque SWP par MITSUI) dans la proportion 95/5. Dans le courant d'air chargĆ© de ces fibres, on ajoute 120 % de poudre hydrorĆ©active du mĆ©lange dĆ©crit Ć  l'exemple 1. L'ensemble est aspirĆ© sur un papier tissue de 18 g/mĀ², calandrĆ© et thermoliĆ© dans un four Ć  une tempĆ©rature de 30 - 150Ā° C pour permettre la fusion des fibres thermoliantes de polyĆ©thylĆØne hydrophobe. Le tout est contrecollĆ©, par colle hotmelt, d'un film polyĆ©thylĆØne sur une face et d'un non-tissĆ© sur l'autre faceIn accordance with the invention, an absorbent complex containing the same hydroreactive material is formed. For this, we defibe pulp of cellulosic fibers (product sold under the brand Rayfloc J by ITT) and synthetic polyethylene pulp (fibers sold under the brand SWP by MITSUI) in the proportion 95/5. In the air stream loaded with these fibers, 120% of hydroreactive powder of the mixture described in Example 1 is added. The whole is sucked on 18 g / mĀ² tissue paper, calendered and thermally bonded in an oven at temperature of 30 - 150 Ā° C to allow the fusion of hydrophobic polyethylene thermobonding fibers. The whole is laminated with hotmelt glue, a polyethylene film on one side and a nonwoven on the other side

On peut Ć©viter de coller un non-tissĆ© en remplaƧant le papier tissue par un non-tissĆ© en fibres bicomposantes polypropylĆØne-polyĆ©thylĆØne (marque Danaklon ES de JACOB HOLM), ce qui permet le liage du non-tissĆ© au matelas absorbant par fusion des matĆ©riaux polyĆ©thylĆ©niques du non-tissĆ© et du matelas absorbant. La nature du non-tissĆ©, le traitement d'enĀ­simage des fibres qui le compose, la tenue de l'ensimage Ć  la chaleur dĆ©terminent la mouillabilitĆ© du produit fini.We can avoid sticking a nonwoven by replacing the tissue paper with a nonwoven made of two-component polypropylene-polyethylene fibers (Danaklon ES brand from JACOB HOLM), which allows the nonwoven to be bonded to the absorbent mattress by melting the materials. polyethylene of nonwoven and absorbent mattress. The nature of the nonwoven, the size treatment of the fibers which compose it, the heat resistance of the size determine the wettability of the finished product.

La composition du produit de 530 g/mĀ² est :

- papier tissueā€‡ā€‡ā€‡ā€‡ā€‡ā€‡18 g/mĀ²
- fibres de celluloseā€‡ā€‡ā€‡ā€‡ā€‡ā€‡200g/mĀ²
- fibres synthĆ©tiquesā€‡ā€‡ā€‡ā€‡ā€‡ā€‡10 g/mĀ²
- poudre hydrorĆ©activeā€‡ā€‡ā€‡ā€‡ā€‡ā€‡250g/mĀ² (47 %)
- adhĆ©sifsā€‡ā€‡ā€‡ā€‡ā€‡ā€‡6 g/mĀ²
- film polyĆ©thylĆØneā€‡ā€‡ā€‡ā€‡ā€‡ā€‡28 g/mĀ²
- non-tissĆ©ā€‡ā€‡ā€‡ā€‡ā€‡ā€‡18 g/mĀ²The composition of the 530 g / mĀ² product is:

- tissue paper 18 g / mĀ²
- cellulose fibers 200g / mĀ²
- synthetic fibers 10 g / mĀ²
- hydroreactive powder 250g / mĀ² (47%)
- adhesives 6 g / mĀ²
- polyethylene film 28 g / mĀ²
- nonwoven 18 g / mĀ²

Un Ć©chantillon de 6 x 10 cm, de 3,2 g, absorbe 16,5 g et sa mouillaĀ­bilitĆ© est de 82 %. L'absorption instantanĆ©e d'une grande quantitĆ© de liquide est lĆ©gĆØrement retardĆ©e ce qui permet une forte absorption caĀ­pillaire.A 6 x 10 cm, 3.2 g sample absorbs 16.5 g and its wettability is 82%. The instantaneous absorption of a large quantity of liquid is slightly delayed which allows a strong capillary absorption.

Le temps de rĆ©action du produit selon l'invention est considĆ©rablement augmentĆ©, 330 minutes, pour une pression maximale inchangĆ©e de 30 cm C. E.. La durĆ©e de rĆ©action est alors de 485 minutes pour cet Ć©chantillon de 3,85 g, contenant 1,85 g de matiĆØre hydrorĆ©active.The reaction time of the product according to the invention is considerably increased, 330 minutes, for an unchanged maximum pressure of 30 cm CE. The reaction time is then 485 minutes for this 3.85 g sample, containing 1.85 g of water-reactive material.

Les mesures d'absorption par capillaritƩ montrent que le mouillage du produit est rƩduit, ce qui permet une hydrolyse douce des rƩactifs, pour une absorption par immersion de 12,6 g (3,3 g de produit).The absorption measurements by capillarity show that the wetting of the product is reduced, which allows a gentle hydrolysis of the reagents, for an absorption by immersion of 12.6 g (3.3 g of product).

Les absorptions selon le troisiĆØme test sont :

51 % : aprĆØs 1 minute
64 % : aprĆØs 10 minutes
64 % : aprĆØs 60 minutesThe absorptions according to the third test are:

51%: after 1 minute
64%: after 10 minutes
64%: after 60 minutes

L'absorption au bout d'une heure est bien infĆ©rieure Ć  75 % de la capaĀ­citĆ©.The absorption after one hour is much less than 75% of the capacity.

EXEMPLE 4EXAMPLE 4

On procĆØde comme Ć  l'exemple 3, mais en introduisant plus de fibres de polyĆ©thylĆØne, 15 % au lieu de 5 %, dans le mĆ©lange fibreux, afin de moduler plus encore la rĆ©activitĆ© du produit.The procedure is as in Example 3, but by introducing more polyethylene fibers, 15% instead of 5%, into the fibrous mixture, in order to further modulate the reactivity of the product.

La composition du produit de 400 g/mĀ² est :

- papier tissueā€‡ā€‡ā€‡ā€‡ā€‡ā€‡18 g/mĀ²
- fibres de cellulose ā€‡ā€‡ā€‡ā€‡ā€‡ā€‡160 g/mĀ²
- fibres synthĆ©tiquesā€‡ā€‡ā€‡ā€‡ā€‡ā€‡24 g/mĀ²
- poudre hydrorĆ©activeā€‡ā€‡ā€‡ā€‡ā€‡ā€‡144 g/mĀ² (36 %)
- adhĆ©sifsā€‡ā€‡ā€‡ā€‡ā€‡ā€‡6 g/mĀ²
- film polyĆ©thylĆØneā€‡ā€‡ā€‡ā€‡ā€‡ā€‡28 g/mĀ²
- non-tissĆ©ā€‡ā€‡ā€‡ā€‡ā€‡ā€‡18 g/mĀ²The composition of the 400 g / mĀ² product is:

- tissue paper 18 g / mĀ²
- cellulose fibers 160 g / mĀ²
- synthetic fibers 24 g / mĀ²
- hydroreactive powder 144 g / mĀ² (36%)
- adhesives 6 g / mĀ²
- polyethylene film 28 g / mĀ²
- nonwoven 18 g / mĀ²

L'absorption d'un Ʃchantillon 6 x 10 cm, de 2,2 g, contenant 0,8 g de mƩlange hydrorƩactif est de 10,6 g et sa mouillabilitƩ n'est plus que de 6 %.The absorption of a 6 x 10 cm 2.2 g sample containing 0.8 g of water-reactive mixture is 10.6 g and its wettability is no more than 6%.

Un Ć©chantillon 7 x 12 cm, de 3,8 g, contenant 1,4 g de mĆ©lange hydroĀ­rĆ©actif dĆ©gaze en 150 minutes pour atteindre la pression maximale de 36 cm CE. L'effet recherchĆ© par l'invention est manifestement atteint, Ć  savoir permettre un dĆ©gagement gazeux progressif, Ć©talĆ© dans le temps. Pour un temps de rĆ©action de 150 minutes, la durĆ©e de rĆ©action est de 300 minutes. Ces valeurs sont manifestement plus Ć©levĆ©es que celles obtenues avec des produits selon l'Ć©tat de la technique.A 3.8 x 7 x 12 cm sample containing 1.4 g of water-reactive mixture degassed in 150 minutes to reach the maximum pressure of 36 cm EC. The effect sought by the invention is clearly achieved, namely to allow a gradual release of gas, spread over time. For a reaction time of 150 minutes, the reaction time is 300 minutes. These values are clearly higher than those obtained with products according to the state of the art.

L'absorption par immersion est de 8,1 g pour un Ʃchantillon de 2,7 g. Les absorptions par montƩe capillaire sont respectivement de :

40 % aprĆØs 1 minute
57 % aprĆØs 10 minutes
57 % aprĆØs 60 minutesThe absorption by immersion is 8.1 g for a sample of 2.7 g. The absorptions by capillary rise are respectively:

40% after 1 minute
57% after 10 minutes
57% after 60 minutes

L'absorption au bout d'une heure ne dƩpasse pas 75 % de la capacitƩ. Elle est infƩrieure Ơ celle du produit ne contenant que 5 % de fibres hydrophobes.The absorption after one hour does not exceed 75% of the capacity. It is lower than that of the product containing only 5% of hydrophobic fibers.

EXEMPLE 5EXAMPLE 5

On opĆØre comme Ć  l'exemple 4, mais le non-tissĆ© recouvrant une face du produit est remplacĆ© par un papier voie sĆØche HOMECEL, dĆ©jĆ  dĆ©crit, de 60 g/mĀ². Il s'agit d'un non-tissĆ© absorbant dont la mouillabilitĆ© est supĆ©rieure Ć  celle de la couche infĆ©rieure comportant des fibres de polyĆ©thylĆØne, SWP.The procedure is as in Example 4, but the nonwoven covering one side of the product is replaced by a HOMECEL dry paper, already described, of 60 g / mĀ². It is an absorbent nonwoven whose wettability is higher than that of the lower layer comprising polyethylene fibers, SWP.

Cet exemple vise Ơ montrer que l'on peut rƩaliser en une ou plusieurs opƩrations des complexes multicouches. D'autres moyens existent pour dƩposer des fibres ou des poudres localement, sous forme de pavƩs par exemple, au sein d'une masse fibreuse.This example aims to show that one can realize in one or more operations multilayer complexes. Other means exist for depositing fibers or powders locally, in the form of blocks for example, within a fibrous mass.

On peut concevoir un complexe oĆ¹ l'agent actif est libĆ©rĆ© par rĆ©action de deux produits A et B dont l'un au moins est hydrorĆ©actif, ces produits A et B Ć©tant placĆ©s judicieusement dans des couches ou des zones diffĆ©rentes de complexe afin d'augmenter l'effet retard.We can conceive a complex where the active agent is released by reaction of two products A and B, at least one of which is water-reactive, these products A and B being placed judiciously in different layers or zones of complex in order to increase the delay effect.

L'absorption d'un Ć©chantillon de 6 x 10 cm, de 2,4 g, contenant 1 g de mĆ©lange hydrorĆ©actif est de 13,7 g et sa mouillabilitĆ©, face HOMECEL, est de 80 %. Cette face est trĆØs hydrophile en regard de la face plus hydrophobe contenant la matiĆØre hydrorĆ©active.The absorption of a 6 x 10 cm 2.4 g sample containing 1 g of water-reactive mixture is 13.7 g and its wettability, on the HOMECEL side, is 80%. This face is very hydrophilic opposite the more hydrophobic face containing the water-reactive material.

Un Ć©chantillon de 7 x 12 cm, contenant 1,3 g environ de matiĆØres hydroĀ­rĆ©actives, atteint en prĆ©sence d'eau la pression maximale de 10 cm CE en un temps de rĆ©action de 1 minute. La durĆ©e de la rĆ©action est supĆ©rieure Ć  300 minutes. La pression restant stable entre 8 et 9 cm C.E.A 7 x 12 cm sample, containing approximately 1.3 g of water-reactive materials, reaches the maximum pressure of 10 cm EC in the presence of water in a reaction time of 1 minute. The reaction time is more than 300 minutes. The pressure remains stable between 8 and 9 cm C.E.

Ce complexe oĆ¹ l'eau se partage entre une zone sans rĆ©actif et une zone rĆ©active permet de limiter le dĆ©gagement gazeux et d'obtenir une durĆ©e de rĆ©action Ć©levĆ©e.This complex where water is divided between a zone without reagent and a reactive zone makes it possible to limit the evolution of gas and to obtain a long reaction time.

Le troisiĆØme test confirme que ce complexe est plus mouillable. L'abĀ­sorption totale Ć©tant de 11,8 g (Ć©chantillon de 2,8 g).The third test confirms that this complex is more wettable. The total absorption being 11.8 g (2.8 g sample).

Les absorptions sont respectivement de :

54 % aprĆØs 1 minute
63 % aprĆØs 10 minutes
66,5 % aprĆØs 60 minutesThe absorptions are respectively:

54% after 1 minute
63% after 10 minutes
66.5% after 60 minutes

L'absorption au bout d'une heure ne dƩpasse pas 75 % de la capacitƩ.The absorption after one hour does not exceed 75% of the capacity.

Ces exemples montrent les avantages des produits selon l'invention comparĆ©s aux produits connus. En effet, les temps d'hydrolyse de la matiĆØre hydrorĆ©active sont ici plus que doublĆ©s ce qui Ć©tait l'effet recherchĆ©, grĆ¢ce Ć  la mise en oeuvre de matiĆØres absorbantes sĆ©lectionĀ­nĆ©es, judicieusement assemblĆ©es.These examples show the advantages of the products according to the invention compared to known products. Indeed, the hydrolysis times of the hydroreactive material are here more than doubled which was the desired effect, thanks to the use of selected absorbent materials, judiciously assembled.

Cet effet est obtenu, selon le procƩdƩ dƩcrit, par l'utilisation de 5 Ơ 15 % de fibres thermoplastiques telles que SWP de MITSUI ou PULPEX de HERCULES.This effect is obtained, according to the method described, by the use of 5 to 15% of thermoplastic fibers such as SWP from MITSUI or PULPEX from HERCULES.

Ce peut ĆŖtre Ć©galement des fibres filĆ©es, coupĆ©es, frisĆ©es ou non, de polyĆ©thylĆØne de DANAKLON ou bicomposantes DANAKLON ES de JACOB HOLM ou encore MELTY d'UNITIKA. Ces fibres sont utilement fondues pour lier le matelas fibreux. L'emploi de poudres thermofusibles, par exemple de polyester Ć  bas point de fusion d'EASTMAN, permet d'obtenir des produits plus souples.It can also be spun fibers, cut, crimped or not, of polyethylene from DANAKLON or two-component DANAKLON ES from JACOB HOLM or even MELTY from UNITIKA. These fibers are usefully fused to bind the fibrous mat. The use of hot-melt powders, for example of polyester with low melting point of EASTMAN, makes it possible to obtain more flexible products.

La matiĆØre hydrophile est composĆ©e de fibres ou mousses naturelles ou rĆ©gĆ©nĆ©rĆ©es, de fibres ou de mousse ou de non-tissĆ© absorbant Ć  base de matiĆØre synthĆ©tique traitĆ©e hydrophile. La mĆŖme matiĆØre partiellement traĆ®tĆ©e peut prĆ©senter les caractĆ©ristiques recherchĆ©es alliant hydropĀ­hilie et hydrophobie.The hydrophilic material is composed of natural or regenerated fibers or foams, fibers or foam or absorbent nonwoven based on hydrophilic treated synthetic material. The same partially treated material may have the desired characteristics combining hydrophilicity and hydrophobicity.

EXEMPLE 6EXAMPLE 6

Selon ce mode de rĆ©alisation, on forme par voie sĆØche, c'est-Ć -dire par voie aĆ©raulique, une nappe de fibres dans un premier temps. On dĆ©pose ensuite la poudre en surface que l'on fait pĆ©nĆ©trer Ć  l'intĆ©rieur de la nappe par un soufflage d'air, une aspiration au travers de l'Ć©paisseur de la nappe, ou enfin une combinaison des deux moyens.According to this embodiment, a sheet of fibers is first formed by a dry route, that is to say by aeraulic route. The powder is then deposited on the surface which is made to penetrate inside the sheet by blowing air, suction through the thickness of the sheet, or finally a combination of the two means.

Cette nappe contenant tout ou partie de la poudre peut ĆŖtre recouverte d'une nappe supplĆ©mentaire, formĆ©e Ć©galement par voie aĆ©rautique, ne contenant pas ou contenant l'autre partie de la poudre hydrorĆ©action.This sheet containing all or part of the powder may be covered with an additional sheet, also formed by air flow, not containing or containing the other part of the hydroreaction powder.

On a ainsi rĆ©alisĆ© une nappe de 300 g/m2 de fibres cellulosiques contenant 20 % de fibres de polyĆ©thylĆØne et incorporant une poudre hydrorĆ©active de mĆŖme composition qu'Ć  l'exemple 1.A sheet of 300 g / m2 of cellulose fibers was thus produced containing 20% of polyethylene fibers and incorporating a water-reactive powder of the same composition as in Example 1.

Cette nappe a Ć©tĆ© thermoliĆ©e par passage au four. On a contrĆ“lĆ© la vitesse de dissolution de l'hydrorĆ©actif en mesurant la vitesse de disĀ­solution de l'hydrorĆ©actif aprĆØs avoir versĆ© 120 cc d'eau sur l'Ć©chanĀ­tillon.This tablecloth was thermobonded by passage in the oven. The rate of dissolution of the water-reactant was monitored by measuring the speed of dissolution of the water-reactive after pouring 120 cc of water onto the sample.

Ainsi, alors que l'hydrorĆ©actif seul produit Ć  l'Ć©quilibre un dĆ©gagement gazeux d'une pression de 16 cm CE dans un temps de rĆ©action de 2 minutes, la nappe rĆ©agit rĆ©guliĆØrement et plus longtemps. La pression du gaz libĆ©rĆ© Ć  l'Ć©quilibre est de 15 cm CE pour un temps de rĆ©action de 12 minutes.Thus, while the hydroreactive alone produces a gaseous evolution at a pressure of 16 cm CE in a reaction time of 2 minutes, the sheet reacts regularly and for a longer time. The pressure of the gas released at equilibrium is 15 cm CE for a reaction time of 12 minutes.

EXEMPLE 7EXAMPLE 7

On rĆ©alise par formation voie sĆØche trois nappes de fibres cellulosiques contenant des fibres synthĆ©tiques SWP Ć  raison de 0 %, 5 % et 15 %, et du percarbonate en poudre. On passe les nappes formĆ©es six secondes au four Ć  150Ā° C.Three layers of cellulosic fibers containing synthetic SWP fibers are produced by dry process at the rate of 0%, 5% and 15%, and powdered percarbonate. The tablecloths formed are passed for six seconds to the oven at 150 Ā° C.

Pour Ć©valuer la vitesse de dissolution de ce sel peroxydĆ© on mesure selon un quatriĆØme test la durĆ©e de dissolution, c'est-Ć -dire le temps mis par un Ć©chantillon, plongĆ© dans de l'eau distillĆ©e, pour obtenir l'Ć©quilibre de la solution du sel dissous dans l'eau, sous agitation. On, constate que les durĆ©es de dissolution du peroxyde sont augmentĆ©es par la prĆ©sence des fibres hydrophobes des produits P5 et P15 ainsi que, comme prĆ©cĆ©demment, les durĆ©es d'hydratation du percarbonate. RĆ©fĆ©rence P 0,5 g percarbonate PO Cellulose + 0,5 g percarbonate P5 Cellulose + 5 % SWP + 0,5 g percarbonate P15 Cellulose + 15 % SWP 0,5 g percarbonate grammage (g/mĀ²) 220 280 310 Test 4 pH initial 5,2 5,2 5,2 5,2 pH d'Ć©quilibre 11,0 11,0 11,0 11,0 durĆ©e de dissolution(s) pH = 10,4 14 38 50 80 To evaluate the dissolution rate of this peroxidized salt, the dissolution time is measured according to a fourth test, that is to say the time taken by a sample, immersed in distilled water, to obtain the balance of the solution of salt dissolved in water, with stirring. It is found that the dissolution times of the peroxide are increased by the presence of the hydrophobic fibers of the products P5 and P15 as well as, as before, the hydration times of the percarbonate. Reference P 0.5 g percarbonate PO Cellulose + 0.5 g percarbonate P5 Cellulose + 5% SWP + 0.5 g percarbonate P15 Cellulose + 15% SWP 0.5 g percarbonate grammage (g / mĀ²) 220 280 310 Test 4 initial pH 5.2 5.2 5.2 5.2 equilibrium pH 11.0 11.0 11.0 11.0 dissolution time (s) pH = 10.4 14 38 50 80

EXEMPLE 8EXAMPLE 8

Comme Ơ l'exemple 7 on rƩalise des mƩlanges contenant de l'acide citrique en poudre Ơ la place du percarbonate.As in Example 7, mixtures containing powdered citric acid are produced in place of percarbonate.

De la mĆŖme maniĆØre, on contrĆ“le la vitesse de dissolution de l'hydrorĀ­Ć©actif acide selon la mĆ©thode du 4ĆØme test, en plongeant l'Ć©chantillon dans de l'eau distillĆ©e prĆ©alablement amenĆ©e Ć  pH 8 avec de la soude. RĆ©fĆ©rence C 0,5 g acid citrique CO Cellulose + 0,5 g acide citrique C5 Cellulose + 5 % SWP + 0,5 g acide citrique C15 Cellulose + 15 % SWP 0,5 g acide citrique grammage (g/mĀ²) 265 280 310 Test 4 pH initial 8,2 8,2 8,2 8,2 pH d'Ć©quilibre 2,6 2,6 2,6 2,6 durĆ©e de dissolution(s) pH = 3,2 10 23 28 ā‰ˆ600 In the same way, the rate of dissolution of the acid hydroreagent is controlled according to the method of the 4th test, by immersing the sample in distilled water previously brought to pH 8 with sodium hydroxide. Reference C 0.5 g citric acid CO Cellulose + 0.5 g citric acid C5 Cellulose + 5% SWP + 0.5 g citric acid C15 Cellulose + 15% SWP 0.5 g citric acid grammage (g / mĀ²) 265 280 310 Test 4 initial pH 8.2 8.2 8.2 8.2 equilibrium pH 2.6 2.6 2.6 2.6 dissolution time (s) pH = 3.2 10 23 28 ā‰ˆ600

Claims (11)

1. Structure absorbante contenant au moins un agent hydrorĆ©actif, destinĆ©e Ć  ĆŖtre disposĆ©e dans un emballage de produits notamment alimentaires, pour en absorber au moins partiellement les liquides, exsudats ou condensats, au contact desquels l'agent rĆ©agit et libĆØre au moins un Ć©lĆ©ment actif, caractĆ©risĆ©e en ce qu'elle est constituĆ©e au moins d'un matelas formĆ© par voie aĆ©raulique d'un mĆ©lange essenĀ­tiellement fibreux de matiĆØres hydrophiles et de matiĆØres hydrophobes Ć  l'intĆ©rieur duquel est rĆ©parti ledit agent hydrorĀ­Ć©actif.1. Absorbent structure containing at least one hydroreactive agent, intended to be placed in a packaging of products, in particular foodstuffs, to absorb at least partially the liquids, exudates or condensates, in contact with which the agent reacts and releases at least one active element , characterized in that it consists at least of a mattress formed by the aeraulic route of an essentially fibrous mixture of hydrophilic materials and hydrophobic materials inside which said hydroreactive agent is distributed. 2. Structure absorbante selon la revendication 1, caractĆ©risĆ©e en ce que les matiĆØres hydrophiles sont des fibres Ć©ventuellement mĆ©langĆ©es Ć  des poudres hydrophiles.2. absorbent structure according to claim 1, characterized in that the hydrophilic materials are fibers optionally mixed with hydrophilic powders. 3. Structure absorbante selon la revendication 2, caractĆ©risĆ©e en ce que les fibres sont cellulosiques telles que fibres de bois, fibres de coton, viscose.3. absorbent structure according to claim 2, characterized in that the fibers are cellulosic such as wood fibers, cotton fibers, viscose. 4. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce que les matiĆØres hydrophobes sont constituĆ©es par des fibres hydrophobes, par un liant, ou par une poudre.4. absorbent structure according to one of the preceding claims, characterized in that the hydrophobic materials are constituted by hydrophobic fibers, by a binder, or by a powder. 5. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce que le matelas, hors agent hydrorĆ©actif, se compose de 5 Ć  60 % de matiĆØres hydrophobes en poids.5. absorbent structure according to one of the preceding claims, characterized in that the mattress, excluding the hydroreactive agent, consists of 5 to 60% of hydrophobic materials by weight. 6. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce que l'agent hydrorĆ©actif est sous forme de poudre, de granulĆ©s, de paillettes, de laminĆ©s, de vermicelles, de fibres.6. Absorbent structure according to one of the preceding claims, characterized in that the hydroreactive agent is in the form of powder, granules, flakes, laminates, vermicelli, fibers. 7. Structure absorbante selon la revendication 6, caractĆ©risĆ©e en ce que l'agent hydrorĆ©actif contenu dans le matelas est dans un rapport en poids compris entre 0,1 et 20 fois celui du matelas hors agent hydrorĆ©actif.7. absorbent structure according to claim 6, characterized in that the hydroreactive agent contained in the mattress is in a weight ratio of between 0.1 and 20 times that of the mattress without hydroreactive agent. 8. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce que le matelas est recouvert, sur au moins l'une de ses faces, d'un voile permĆ©able ou bien d'une pellicule imperĀ­mĆ©able.8. Absorbent structure according to one of the preceding claims, characterized in that the mattress is covered, on at least one of its faces, with a permeable veil or else with an impermeable film. 9. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce que le matelas est stabilisĆ© au moyen d'un liant.9. absorbent structure according to one of the preceding claims, characterized in that the mattress is stabilized by means of a binder. 10. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, caractĆ©risĆ©e en ce qu'elle comporte un deuxiĆØme matelas fibreux prĆ©sentant une plus grande mouillabilitĆ© que le premier matelas.10. Absorbent structure according to one of the preceding claims, characterized in that it comprises a second fibrous mattress having greater wettability than the first mattress. 11. Structure absorbante selon l'une des revendications prĆ©cĆ©dentes, l'agent hydrorĆ©actif Ć©tant constituĆ© de deux composants au moins, caractĆ©risĆ©e en ce qu'elle comporte au moins deux couches ou deux matelas fibreux, chacun contenant un des composants de l'agent hyĀ­drorĆ©actif.11. absorbent structure according to one of the preceding claims, the water-reactive agent consisting of at least two components, characterized in that it comprises at least two layers or two fibrous mat, each containing one of the components of the water-reactive agent .
EP88402425A 1987-09-29 1988-09-27 Absorbent pad for packaging Expired - Lifetime EP0310489B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88402425T ATE62198T1 (en) 1987-09-29 1988-09-27 ABSORBENT PACKAGING ELEMENT.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8713410 1987-09-29
FR8713410A FR2621015B1 (en) 1987-09-29 1987-09-29 ABSORBENT STRUCTURE FOR PACKAGING

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EP0310489A1 true EP0310489A1 (en) 1989-04-05
EP0310489B1 EP0310489B1 (en) 1991-04-03

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EP (1) EP0310489B1 (en)
JP (1) JPH02501379A (en)
AT (1) ATE62198T1 (en)
BR (1) BR8807206A (en)
CA (1) CA1314699C (en)
DE (1) DE3862278D1 (en)
DK (1) DK256789D0 (en)
ES (1) ES2021451B3 (en)
FI (1) FI91735C (en)
FR (1) FR2621015B1 (en)
GR (1) GR3002100T3 (en)
PT (1) PT88595B (en)
WO (1) WO1989002861A1 (en)

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* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
CA2332843A1 (en) 1998-06-02 1999-12-09 Thomas Erick Snowball Carbon dioxide atmosphere modifiers for packaging

Citations (3)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
US1909013A (en) * 1932-05-27 1933-05-16 Francis W Ruzicka Distributing package for perishables
US4275811A (en) * 1979-08-23 1981-06-30 Cellu Products Company Receptacle for containing and displaying food products
EP0138545A2 (en) * 1983-10-11 1985-04-24 Michelsen Packaging Company Atmosphere control cushioning pad, method of manufacture, and use

Patent Citations (3)

* Cited by examiner, ā€  Cited by third party
Publication number Priority date Publication date Assignee Title
US1909013A (en) * 1932-05-27 1933-05-16 Francis W Ruzicka Distributing package for perishables
US4275811A (en) * 1979-08-23 1981-06-30 Cellu Products Company Receptacle for containing and displaying food products
EP0138545A2 (en) * 1983-10-11 1985-04-24 Michelsen Packaging Company Atmosphere control cushioning pad, method of manufacture, and use

Also Published As

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FI892533A0 (en) 1989-05-24
EP0310489B1 (en) 1991-04-03
CA1314699C (en) 1993-03-23
DK256789A (en) 1989-05-26
ATE62198T1 (en) 1991-04-15
PT88595B (en) 1993-10-29
FI892533L (en) 1989-05-24
WO1989002861A1 (en) 1989-04-06
DE3862278D1 (en) 1991-05-08
FR2621015B1 (en) 1989-12-01
FI91735B (en) 1994-04-29
FI91735C (en) 1994-08-10
DK256789D0 (en) 1989-05-26
BR8807206A (en) 1989-10-17
JPH02501379A (en) 1990-05-17
ES2021451B3 (en) 1991-11-01
PT88595A (en) 1989-07-31
FR2621015A1 (en) 1989-03-31
GR3002100T3 (en) 1992-12-30

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