EP3383989B1 - Coated detergent tablet - Google Patents

Coated detergent tablet Download PDF

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Publication number
EP3383989B1
EP3383989B1 EP16819597.2A EP16819597A EP3383989B1 EP 3383989 B1 EP3383989 B1 EP 3383989B1 EP 16819597 A EP16819597 A EP 16819597A EP 3383989 B1 EP3383989 B1 EP 3383989B1
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EP
European Patent Office
Prior art keywords
tablet
water
detergent tablet
agent
weight
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.)
Active
Application number
EP16819597.2A
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German (de)
French (fr)
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EP3383989A1 (en
Inventor
Valerie Venet
Jacques Brosse
Sandrine ARNAUD
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Eurotab SA
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Eurotab SA
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Priority to PL16819597T priority Critical patent/PL3383989T3/en
Publication of EP3383989A1 publication Critical patent/EP3383989A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0082Coated tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2065Polyhydric alcohols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C11D2111/14

Definitions

  • the present invention relates to the field of detergent tablets, especially detergent tablets for dishwashers.
  • Detergents in tablet form have many advantages over other detergents, in the form of liquid or powder, in particular as regards dosing, storage or transport.
  • Detergent tablets are most often prepared by premixing various components preferably in the form of powder or granules but also in liquid form. This premix is then compacted using a press to form a tablet. Industrially, rotary presses are preferably used to form compacted tablets at high rates.
  • multilayer tablets make it possible both to separate the components that can react with each other, and to only compress the compression-sensitive components once by inserting them into the last layer.
  • Multilayer tablets may exhibit slightly delayed disintegrations between different layers, the first layer having been compressed several times thus generally has a longer disintegration than subsequent layers less compressed.
  • EP 2 196 531 discloses a coating for detergent tablets, such as dishwasher tablets, for increasing the stability and strength of the tablet, said coating being water-soluble and containing at least one graft copolymer of polyvinyl alcohol and polyethylene glycol.
  • a detergent tablet formed from at least one active detergent and a detergency builder, and being coated with a coating formed from a water-soluble organic polymer, such as a copolymer of acrylate and maleate.
  • the coatings proposed in these documents for coating the detergent tablets are intended to increase the stability of said tablets by forming a layer which mechanically maintains the compacted detergent composition.
  • they are complex to implement may denature the action of the detergent tablet or reduce the effectiveness and / or disintegration of the detergent tablet.
  • An object of the present invention is to provide a detergent tablet, especially for dishwasher application, having improved efficiency, mechanical strength and stability allowing the tablet to be handled and stored without undergoing degradation.
  • An object of the present invention is also to provide a detergent tablet, especially for dishwashing application, having an improved action while having a manufacturing method simple to implement.
  • a detergent tablet comprising a body formed from compacted powder, said body being coated with a water-soluble coating, said water-soluble coating having a composition comprising a film-forming agent and water, characterized in that the The composition of the water-soluble coating further comprises at least one specific agent to improve the rinsing efficacy of the detergent tablet.
  • a detergent product is therefore proposed in the form of a coated tablet, also called a coating, formed of a water-soluble solution, making it possible to cover the surface of the tablet by forming a homogeneous film adhering to the surface of the tablet.
  • the detergent product in tablet form may for example be a dishwashing detergent.
  • the detergent tablet proposed comprises a body formed for example from compacted powder, said body being coated with a water-soluble coating.
  • the water-soluble coating used has a composition comprising a film-forming agent and water, and has the particularity of further comprising at least one specific agent to improve the rinsing efficiency of the detergent tablet.
  • the composition of the water-soluble coating may also comprise a humectant.
  • the specific agent used to improve the rinsing efficacy of the detergent tablet is preferably selected from compounds having an "anti-spottingā€ action (which could also be described as anti-trace action) and / or action "anti-filming" (which could also be called anti-film action).
  • spotting is meant any trace on a dishware element, caused by the drying of drops of water on the surface of the material forming the dishware, in particular glass.
  • Calcium and magnesium present in water can for example be deposited on the surface of the glass and form traces during drying in the dishwasher. The higher the water hardness, the higher the amount of calcium and magnesium ions it contains.
  • Frming means any appearance of a film / white deposit on all or a large part of the surface of the material forming the dishware, in particular the opacification of the glass.
  • the calcium and magnesium ions present in the water can for example form deposits of limestone more or less uniform on the surface of the glass.
  • the use of a specific agent intended to improve the rinsing efficiency of the detergent tablet, such as an anti-spotting and / or anti-filming agent, in the composition forming the coating coating the detergent tablet allows for increased stability over existing coated tablets.
  • Providing such a specific agent in the composition forming the coating coating the detergent tablet is also particularly advantageous since it makes it possible to use in particular agents generally being in liquid form and which are therefore difficult to use in tablet detergent formulations.
  • specific agents in liquid form are generally difficult to introduce into the powder mixture to be compacted, and further cause problems of stability of the final compacted tablet, especially because of the water present in such agents specific in liquid form that can react with other raw materials of the detergent formula.
  • the detergent product used is preferably in the form of a tablet which has sufficient cohesion to be handled without being broken and which easily disintegrates in water.
  • the tablet does not require a high hardness, its cohesion and mechanical strength being enhanced by the use of a coating coming to coat the tablet, that is to say adhere to the surface of the tablet.
  • the tablet has a body formed by compaction for example, in particular from a mixture of raw materials in the form of powder or granules, but also in liquid form.
  • the detergent tablets consist of a mixture of components comprising different actions, these components may for example be chosen from surfactants, fillers, sequestering agents, bleaching agents, enzymes, bleaching activators, alkaline agents, polymers, perfumes, dyes.
  • the detergent tablet may consist of a single layer or a stack of several layers that are superimposed on each other, forming a uniform and compact block.
  • the different layers may have the same or different composition.
  • the tablet preferably has an elongated shape with a section having any shape, for example circular, oval, octagonal, or parallelepipedal.
  • the corners of the tablet can be curved so that they are less brittle.
  • Each layer preferably has the same section so that the stack of layers forms a uniform tablet.
  • the detergent tablet preferably has a mass of between 1 gram and 100 grams, and more preferably between 5 grams and 60 grams.
  • the tablet preferably has a mechanical strength of between 5 Newtons and 300 Newtons, and more preferably between 10 Newtons and 90 Newtons.
  • the manufacturing process used generally consists of progressively forming a complex of several layers and compacting this complex with each new addition of layer so as to solidify the tablet.
  • the tablets are manufactured by direct compression with a hydraulic press or a rotary press, especially when it is desired to form tablets at an industrial rate.
  • the first step is therefore to mix the components intended to form the compositions corresponding to each of the layers.
  • the mixture corresponding to the first layer is introduced into the matrix and then pre-compacted to form the first layer.
  • the mixture of the second layer is then introduced into the matrix on the first layer and then pre-compacted as for the first layer, in the same way the other layers of the tablet are introduced into the matrix.
  • the set of layers is then compacted to obtain a shock-resistant tablet.
  • the pre-compaction forces used are preferably between 0 kN and 100 kN (kilonewtons), and more preferably between 0 kN and 50 kN.
  • the compression force used for the final compaction is preferably between 5 kN and 200 kN, and more preferably between 10 kN and 100 kN.
  • a dishwasher detergent tablet includes a combination of one or more of the components described in more detail below, without being limiting thereto.
  • the tablet preferably contains enzymes to form an enzymatic system.
  • enzymes are for example chosen from proteases, amylases, lipases, and combinations thereof.
  • These enzymes are generally in the form of granules that contain a certain amount of active enzymes.
  • the detergent tablets that are preferably used have an overall composition integrating enzymes whose total amount of active enzymes is between 0.003% and 5% by weight, and preferably between 0.003% and 2% by weight.
  • Amylases can be used to decompose starch-based stains, such as, for example, the product dispensed by Genencor under the reference "Powerase 16000HSā€.
  • the tablet may also contain proteases to act on protein tasks such as meat and eggs.
  • proteases to act on protein tasks such as meat and eggs.
  • the tablet may also contain lipases to improve the breakdown of grease stains on the dishes.
  • the tablet preferably contains a bleaching agent, that is to say a substance capable of directly or indirectly oxidizing the organic compounds described.
  • the bleaching agents may be of the sodium perborate mono or tetrahydrate type, sodium percarbonate, sodium persilicate, and sodium persulfate.
  • the tablet preferably comprises between 1% and 50% by weight of bleaching agent, and more preferably between 5% and 20% by weight.
  • the tablet preferably contains a tetraacetylenediamine (TAED), pentaacetylglucose (PAG), tetraacethylglycoluryl (TAGU) and sodium benzoloxybenzene sulfonate bleach activator.
  • TAED tetraacetylenediamine
  • PAG pentaacetylglucose
  • TAGU tetraacethylglycoluryl
  • sodium benzoloxybenzene sulfonate bleach activator sodium benzoloxybenzene sulfonate bleach activator.
  • the tablet preferably comprises between 0.5% and 40% by weight activator of the bleaching agent, and more preferably between 1% and 10% by weight.
  • the tablet comprises a ratio between bleaching agents and bleach activators corresponding to a molar ratio of 6 to 1, more preferably a molar ratio of 5 to 1.
  • the tablet may also contain catalysts to improve the effectiveness of agents on oxidizable stains. Mention may be made, for example, of manganese catalysts such as the product referred to as "Peractive FDO X" marketed by Weylchem.
  • Detergent additives trap metal ions such as calcium and magnesium present in the wash solution by complexation, ion exchange or precipitation.
  • Detergent adjuvants are preferably present in an amount of from 5% to 99% by weight, and more preferably from 10% to 50% by weight.
  • Non-phosphorus water soluble builders can be organic or inorganic.
  • the inorganic compounds that may be present are chosen from zeolites, phyllosilicates, alkali metal carbonates (generally sodium), and sodium silicates, mixtures of sodium carbonate and sodium silicates, such as the product referenced "questlock Distributed by the company Amcol.
  • the organic compounds that may be present are chosen from polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, mono-, di- and glycerol tri-succinates, carboxymethyloxysuccinates, polycarboxylic amino compounds such as methylglycinediacetate (MGDA) carboxymethyloxymalonates, glutamic diacetic acid (GLDA), imminodisuccinate (IDS), ethylenediamine disuccinate (EDDS), dipicolinates, nitrilotriacetates and hydroxyethyliminodi acetates.
  • polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, mono-, di- and
  • MGDA methylglycinediacetate acid
  • the class of water-soluble phosphorus adjuvants includes orthophosphates, methaphosphates, pyrophosphates and alkali metal polyphosphates.
  • inorganic phosphorus detergency builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Sodium tripolyphosphate is a particularly preferred phosphorus adjuvant for dishwasher tablets. It exists in hydrated, anhydrous or partially hydrated form, and mixtures of these forms can be used to regulate the rate of disintegration and dissolution of the tablet.
  • the pH of the wash solution must be at least 9 and preferably between 9.5 and 12.5.
  • Most detergency builders are alkaline, so there is no need to add other compounds to the tablet to adjust the pH.
  • the tablet preferably contains one or more nonionic surfactants, for example low foaming nonionic surfactants.
  • the surfactants are amphiphilic molecules, which are composed of an apolar lipophilic part and a polar hydrophilic part.
  • the amount of surfactants in the tablet is preferably in the range of 0.05% to 20% by weight, and more preferably in the range of 1% to 5% by weight.
  • surfactants in solid form are easier to use in tablets which also have solid compositions.
  • the surfactant when it is in liquid form, it can also be introduced into the tablet, in which case it is adsorbed on supports such as sodium carbonate or silica.
  • the synthetic nonionic surfactants may be generally defined as compounds derived from the condensation between alkylene oxide groups and hydrophobic organic compounds, which may be aliphatic or aromatic.
  • the length of the hydrophilic portion of the surfactant can be easily adjusted to obtain a water-soluble compound having the desired HLB, the HLB translating the degree of hydrophilicity or lipophilicity of the surfactant.
  • anionic surfactants especially to improve the drying of dishes for dishwasher tablets.
  • the amount of anionic surfactants present in the tablet is preferably between 0.05% and 40% by weight, and preferably between 1% and 20% by weight.
  • this may include additional components that will be used according to the desired specificities of the detergent tablet.
  • protective additives such as benzotriazole and zinc salts may be used. These additives form a dishwashing and dishwasher protection system against unwanted chemical attack from either component of the tablet.
  • Chelating agents for trapping metal ions may also be present in the composition. They are also known as sequestering agents or complexing metal ions. If necessary, it is preferable that the amount of chelating agents is of the order of 0.5% to 20% by weight, and preferably 0.5% to 5% by weight.
  • Preferred chelating agents include organic phosphonates, amino carboxylates, polyfunctionally substituted compounds, and mixtures thereof. It is also possible to use homopolymers of acrylic acid or copolymers of acrylic and maleic acid.
  • bursting agents which are intended to accelerate the disintegration of the layer in which they are incorporated.
  • Preferred bursting agents include carboxymethylcellulose, crosslinked carboxymethylcellulose, croscarmellose sodium, cellulose, polyvinylpyrrolidone and mixtures thereof.
  • Dyes can also be added to differentiate the layers from each other. These dyes are essentially intended to improve the aesthetic appearance of the tablet vis-Ć -vis the consumer.
  • binders that can increase the hardness of the pellet and reduce its friability.
  • binders include polyethylene glycol.
  • Lubricants can also be used to facilitate ejection of the tablet at the output of the rotary press.
  • lubricants that can be used include alkali metal stearates such as calcium stearate and magnesium stearate.
  • additives could be used such as anti-foaming agents.
  • the main body constituting the detergent tablet is formed, a particular solution is used to form the water-soluble coating, or coating, intended to cover the surface of the tablet.
  • this coating coming to coat the body of the detergent tablet has other advantages than that of protecting the body against shocks and against the humidity present in the ambient air. Indeed, he is going allow for example to improve the action of the detergent tablet, particularly with regard to rinsing. It will also participate in the overall stability of the detergent tablet while providing better disintegration and low friability of the body.
  • the solution used to form the water soluble coating contains a film forming agent, water and a specific agent to improve the rinsing efficiency of the detergent tablet.
  • the solution may for example comprise polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the PVAs that can be used preferably have a degree of hydrolysis greater than or equal to 40% (mol%), preferably between 70% and 98% (mol%), and more preferably a degree of hydrolysis between 80% and 90%.
  • the PVAs used preferably have a molar mass (Mw) of between 10,000 g / mol and 200,000 g / mol, and more preferably between 15,000 g / mol and 100,000 g / mol.
  • Mw molar mass
  • the mass molar mass of the PVA strongly impacts the final viscosity of the coating solution.
  • the coating solution may contain PVA in a proportion of between 5% and 80% by weight relative to the total weight of the coating solution, preferably between 20% and 60% by weight relative to the total weight of the coating solution. coating, and more preferably between 30% and 55% by weight relative to the total weight of the coating solution.
  • a humectant may further be used in the solution to form the water-soluble coating. Humectants especially prevent water from migrating into the tablet.
  • Such a humectant is for example selected from glycerine, polyethylene glycol, and their combination.
  • the coating solution may contain humectants in a proportion of less than or equal to 25% by weight relative to the total weight of the coating solution, preferably in a proportion of between 1% and 20% by weight relative to the total weight. of the coating solution, and more preferably a proportion of between 2% and 10% by weight relative to the total weight of the coating solution.
  • the specific agent for improving the rinsing efficiency is preferably an anti-spotting and / or anti-filming agent.
  • the anti-spotting agents make it possible to eliminate or limit the appearance of spotting, that is to say traces, in particular by avoiding the nucleation of drops of water on the surface of the glass or dishes.
  • the anti-filming agents make it possible to limit or eliminate the appearance of filming, that is to say the appearance of a film or white deposit.
  • the coating solution preferably contains specific agents in a proportion of between 0.05% and 50% by weight relative to the total weight of the coating solution, and more preferably between 2% and 20% by weight relative to the total weight of the coating solution.
  • the specific agents for improving the rinsing efficiency are specific polymers, preferably polymers having an anti-spotting and / or anti-filming action.
  • an anti-spotting agent it is possible for example to choose a compound from carboxylate polymers, hydrophobic modified carboxylate polymers, in particular HASE polymers, and combinations thereof.
  • carboxylate polymers hydrophobic modified carboxylate polymers, in particular HASE polymers, and combinations thereof.
  • HASE polymers hydrophobic modified carboxylate polymers
  • one of the products marketed by the Dow Chemical Company can be used under the references ā€œacusol 820", ā€œacusol 460ā€ or "acusol 460NDā€.
  • an anti-spotting agent it is also possible to choose a compound among the hydrophobic modified acrylic / styrene copolymers.
  • an anti-filming agent one can for example choose a compound among the copolymers of acrylic acid and of sulfonated monomer.
  • an anti-filming agent it is also possible to choose a compound among the copolymers of acrylic acid and of sulfonic acid.
  • acusol 588G the product marketed by Dow Chemical under the reference ā€œacusol 588Gā€ may be used.
  • an anti-filming agent it is also possible to choose a compound among the copolymers of acrylic acid and maleic acid.
  • acusol 497NG marketed by Dow Chemical
  • alcosperse175ND marketed by AkzoNobel
  • Sokalan CP42 marketed by BASF.
  • the coating solution may also contain a bittering agent such as denatonium benzoate and / or perfume.
  • the rest of the solution is water.
  • the various compounds are mixed at room temperature to form the solution for forming the coating of the detergent tablet.
  • the resulting mixture is for example sprayed on the surface of the body forming the detergent tablet, preferably at room temperature using a nozzle system.
  • the thickness of the coating deposited on the surface of the detergent tablet is for example between 0.05 ā‡ m and 1000 ā‡ m, preferably between 5 ā‡ m and 300 ā‡ m, and more preferably between 15 ā‡ m and 150 ā‡ m.
  • the water-soluble coating deposited on the tablet preferably represents between 0.5% and 15% of the total mass of the detergent tablet, and more preferably between 2% and 5% of the mass of the tablet.
  • Test 1 Spraying the coating solution on a tablet
  • the objective of this test is to compare the disintegration time and friability of a coated tablet, that is to say coated with a water-soluble coating, and a non-coated tablet, that is to say say without coating.
  • the different layers of the tablet are compressed on a hydraulic press so as to form a tablet having an overall mass of 16 g.
  • the pre-compression and compression forces used are shown in Table 3 below.
  • the composition of the solution to form the water-soluble coating is summarized in Table 2 below.
  • a uniform coating with a total mass of 0.4 g is deposited on the surface of the tablet so as to form a coating.
  • Table 2 ā‡ / i> Raw material Coating solution (% by weight) Polyvinyl alcohol 45.84 Water 47.91 Glycerin 0 Acusol 460 ND 6.25
  • the hardness of the tablets was measured on an MTS durometer.
  • the disintegration time of the tablets obtained was measured on equipment that goes back and forth with a frequency of 60 strokes / min.
  • the shelves are placed in a basket with multiple holes to let the water through.
  • the baskets are then soaked in 1.8L beakers of water at 30 Ā° C.
  • the disintegration time is noted a once the tablet is completely disintegrated and there are no more tablet residues in the basket.
  • Test 2 Use of an anti-spotting agent in the coating solution to improve the rinsing efficiency of a dishwasher tablet
  • the objective of this test is to evaluate the influence of the use of a coating incorporating an anti-spotting agent on the rinsing efficiency of the tablets.
  • the anti-spotting agent used for this comparative test is the product referred to as "acusol 460NDā€ marketed by Dow Chemical.
  • the compounds used in the formula of each tablet are divided into three layers.
  • the compounds of the different layers are shown in Tables 4a, 4b and 4c below.
  • a coating solution is sprayed on the surface of tablets thus formed to coat the tablet with a water-soluble coating.
  • Table 5 specifies the composition of the coating solution used for these tablets No. 4, No. 5, No. 6 and No. 7. ā‡ i> Table 5 ā‡ / i> Ingredients solution coating Tablet # 4 (% by weight) Tablet # 5 (% by weight) Tablet # 6 (% by weight) Tablet # 7 (% by weight) Polyvinyl alcohol 47,90 47,90 45.84 45.84 Water 52.10 50,10 47.91 46.91 Glycerin 0 2.00 0 1.00 Acusol 460 ND 0 0 6.25 6.25 TOTAL 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
  • Each of tablets No. 3, No. 4, No. 5, No. 6 and No. 7 thus manufactured comprise the same amount of anti-spotting agent, namely 0.029 g of "Acusol 460 ND" product.
  • Table 6 summarizes the manufacturing parameters of the different tablets, and gives the measurements of hardness and disintegration of each of the tablets, it being understood that these parameters were measured in the same way as for the test 1.
  • Table 6 ā‡ i> Table 6 ā‡ / i> Tablet n Ā° 3 Tablet n Ā° 4 Tablet n Ā° 5 Tablet n Ā° 6 Tablet n Ā° 7 Mass layer 1 (g) 6 6 6 6 6 Mass layer 2 (g) 5 5 5 5 5 Mass layer 3 (g) 5 5 5 5 5 5 5
  • the tests to measure the rinsing efficiency of the tablets were carried out with a Fagor LFF-041 dishwasher programmed in a short wash cycle (30 minutes) at 35 Ā° C and a water hardness of 35 Ā° C. TH.
  • the rinsing efficiency of the tablets is evaluated by observation of the glasses using a box with spots.
  • Spotting is measured after a wash cycle. Spotting is rated on a scale of scores between 0 and 7, where 0 is the worst score (ineffective rinse) and 7 is the best rating (very effective rinse).
  • the filming is measured after 5 successive washing cycles. The filming is evaluated by observation of the veil present on the glasses. Filming is rated with a rating scale between 0 and 10, where 0 is the worst rating (ineffective rinsing) and 10 is the best rating (very effective rinsing).
  • the gloss is evaluated after 1 wash cycle.
  • the brilliance is evaluated thanks to the scale of notes of 0 to 10, where 0 is the worst note (ineffective rinsing) and 10 is the best note (rinsing very effective).
  • the addition of the anti-spotting agent (Acusol 460 ND) in the coating solution therefore makes it possible to increase the rinsing efficiency on the short cycle spotting.
  • the rapid dispersion of the anti-spotting agent (Acusol 460 ND) in the washing solution makes it possible to improve the efficiency on the spotting of the tablet.
  • Test 3 Use of an anti-spotting polymer in the coating solution to improve the stability of a dishwasher tablet
  • the objective of this test is to evaluate the influence of the use of a coating incorporating an anti-spotting agent on the shelf stability.
  • the anti-spotting agent used for this comparative test is the product referred to as "acusol 460NDā€ marketed by Dow Chemical.
  • the compounds used in the formula of each tablet are divided into three layers.
  • the compounds of the different layers are shown in Tables 8a, 8b and 8c below.
  • Each of the manufactured tablets # 8 are individually wrapped in a water-soluble flowpack.
  • a water-soluble flowpack is a package formed from polyvinyl alcohol, of thickness 35 ā‡ m, such as for example the product referenced "L711" marketed by the company MonoSol.
  • a coating solution is sprayed on the surface of tablets thus formed to coat the tablet with a water-soluble coating.
  • a uniform coating of 0.5 g coating solution is deposited on the surface of the tablet to form a uniform coating.
  • Table 9 specifies the composition of the coating solution used for these tablets No. 9, No. 10, No. 11 and No. 12. ā‡ i> Table 9 ā‡ / i> Ingredients solution coating Tablet n Ā° 9 (% in mass) Tablet # 10 (% by weight) Tablet n Ā° 11 (% in mass) Tablet # 12 (% by weight) Polyvinyl alcohol 47,90 47,90 45.84 45.84 Water 52.10 50,10 47.91 46.91 Glycerin 0 2.00 0 1.00 Acusol 460 ND 0 0 6.25 6.25 TOTAL 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
  • Table 10 summarizes the manufacturing parameters of the various tablets, and gives the measurements of hardness and disintegration of each of the tablets, it being understood that these parameters were measured in the same way as for the test 1.
  • Table 10 ā‡ i> Table 10 ā‡ / i> Tablet n Ā° 8 Tablet n Ā° 9 Tablet n Ā° 10 Tablet n Ā° 11 Tablet n Ā° 12
  • Each flexible bag containing the 5 copies of each of the different tablets is then placed in a climatic chamber at 38 Ā° C. and 70% relative humidity for 2 weeks.
  • each tablet is tested to examine the visual appearance and measure the disintegration time of each type of tablet.
  • disintegration time tablets 11 and 12 is consistent and substantially identical to the disintegration time of other types of tablets.

Description

DOMAINE DE L'INVENTIONFIELD OF THE INVENTION

La prƩsente invention concerne le domaine des tablettes dƩtergentes, notamment les tablettes dƩtergentes pour lave-vaisselle.The present invention relates to the field of detergent tablets, especially detergent tablets for dishwashers.

ETAT DE LA TECHNIQUESTATE OF THE ART

Les dƩtergents sous forme de tablettes prƩsentent de nombreux avantages par rapport aux autres dƩtergents, sous forme de liquide ou poudre, notamment en ce qui concerne le dosage, le stockage ou encore le transport.Detergents in tablet form have many advantages over other detergents, in the form of liquid or powder, in particular as regards dosing, storage or transport.

Les tablettes dƩtergentes sont le plus souvent prƩparƩes en prƩ-mƩlangeant divers composants prƩfƩrentiellement sous forme de poudre ou granulƩ mais Ʃgalement sous forme liquide. Ce prƩ-mƩlange est ensuite compactƩ Ơ l'aide d'une presse pour former une tablette. Industriellement, on utilise de prƩfƩrence des presses rotatives pour permettre de former des tablettes compactƩes Ơ hautes cadences.Detergent tablets are most often prepared by premixing various components preferably in the form of powder or granules but also in liquid form. This premix is then compacted using a press to form a tablet. Industrially, rotary presses are preferably used to form compacted tablets at high rates.

Le domaine de la dĆ©tergence impose des contraintes particuliĆØres pour former des tablettes puisque certains composants supportent mal la compression, d'autres composants peuvent rĆ©agir entre eux avant l'utilisation et ainsi diminuer l'efficacitĆ© de la tablette lors de l'utilisation, et c'est pourquoi les tablettes multicouches ont Ć©tĆ© dĆ©veloppĆ©es. En effet, de telles tablettes multicouches permettent Ć  la fois de sĆ©parer les composants susceptibles de rĆ©agir entre eux, et de ne compresser qu'une seule fois les composants sensibles Ć  la compression en les insĆ©rant dans la derniĆØre couche. Les tablettes multicouches peuvent prĆ©senter des dĆ©litements lĆ©gĆØrement diffĆ©rĆ©s entre les diffĆ©rentes couches, la premiĆØre couche ayant Ć©tĆ© compressĆ©e plusieurs fois prĆ©sente ainsi gĆ©nĆ©ralement un dĆ©litement plus long que les couches suivantes moins compressĆ©es.The field of detergency imposes particular constraints to form tablets since some components poorly support compression, other components can react with each other before use and thus reduce the effectiveness of the tablet during use, and c This is why multilayer tablets have been developed. In fact, such multilayer tablets make it possible both to separate the components that can react with each other, and to only compress the compression-sensitive components once by inserting them into the last layer. Multilayer tablets may exhibit slightly delayed disintegrations between different layers, the first layer having been compressed several times thus generally has a longer disintegration than subsequent layers less compressed.

L'une des problĆ©matiques rĆ©currentes dans le domaine des tablettes dĆ©tergentes est la rĆ©sistance de ces tablettes dans le temps, notamment pour qu'elles puissent ĆŖtre manipulĆ©es et transportĆ©es sans qu'elles ne se dĆ©sagrĆØgent ou se dĆ©sintĆØgrent.One of the recurring problems in the field of detergent tablets is the resistance of these tablets over time, in particular so that they can be handled and transported without them disintegrating or disintegrating.

A cet Ć©gard, il a Ć©tĆ© proposĆ© d'enrober les tablettes dĆ©tergentes d'un revĆŖtement ou d'une pellicule, que l'on appelle Ć©galement Ā« coating Ā» selon le terme anglo-saxon, pour renforcer la rĆ©sistance des tablettes. On retrouve par exemple de tels enseignements dans un brevet de la sociĆ©tĆ© Colgate Palmolive publiĆ© en 1966 sous la rĆ©fĆ©rence US 3,231,505 , oĆ¹ il est proposĆ© de revĆŖtir la tablette dĆ©tergente d'une pellicule de polymĆØre organique synthĆ©tique, par exemple de l'alcool polyvinylique (ou PVA selon l'acronyme anglais de polyvinyl alcool), afin d'augmenter la rĆ©sistance Ć  l'abrasion et Ć  une rupture accidentelle de la tablette.In this regard, it has been proposed to coat the detergent tablets with a coating or a film, which is also called "coating" according to the Anglo-Saxon term, to strengthen the strength of the tablets. For example, such teachings are found in a patent of the company Colgate Palmolive published in 1966 under the reference US 3,231,505 , where it is proposed to coat the detergent tablet with a film of synthetic organic polymer, for example polyvinyl alcohol (or PVA according to the acronym of polyvinyl alcohol), in order to increase the resistance to abrasion and accidental breakage of the tablet.

De maniĆØre semblable, la demande internationale de PROCTER & GAMBLE publiĆ©e en 2001 sous la rĆ©fĆ©rence WO 01/64829 porte sur l'enrobage de tablettes dĆ©tergentes avec un revĆŖtement dispersable dans l'eau composĆ© par exemple de PVA, pour permettre de produire des tablettes ayant une soliditĆ© et une rĆ©sistance mĆ©canique semblables aux tablettes traditionnelles tout en Ć©tant moins compactĆ©es et donc pouvant ĆŖtre dissoutes plus rapidement.Similarly, the international application of PROCTER & GAMBLE published in 2001 under the reference WO 01/64829 relates to the coating of detergent tablets with a water-dispersible coating composed for example of PVA, to enable the production of tablets having a strength and a mechanical strength similar to traditional tablets while being less compacted and therefore capable of being dissolved more quickly.

Un autre brevet, au nom de Dalli-Werke GmbH et Co. KG, publiĆ© sous la rĆ©fĆ©rence EP 2 196 531 , dĆ©crit un revĆŖtement pour des tablettes dĆ©tergentes, telle que les tablettes lave-vaisselle, permettant d'augmenter la stabilitĆ© et la rĆ©sistance mĆ©canique de la tablette, ledit revĆŖtement Ć©tant soluble dans l'eau et contenant au moins un copolymĆØre greffĆ© d'alcool polyvinylique et de polyĆ©thylĆØne glycol.Another patent, on behalf of Dalli-Werke GmbH and Co. KG, published under reference EP 2 196 531 discloses a coating for detergent tablets, such as dishwasher tablets, for increasing the stability and strength of the tablet, said coating being water-soluble and containing at least one graft copolymer of polyvinyl alcohol and polyethylene glycol.

Dans le brevet US 5,916,866 , il est proposĆ© une tablette dĆ©tergente formĆ©e Ć  partir d'au moins un agent dĆ©tergent actif et d'un adjuvant de dĆ©tergence, et Ć©tant enrobĆ©e d'un revĆŖtement formĆ© Ć  partir d'un polymĆØre organique soluble dans l'eau, tel qu'un copolymĆØre d'acrylate et de malĆ©ate.In the patent US 5,916,866 there is provided a detergent tablet formed from at least one active detergent and a detergency builder, and being coated with a coating formed from a water-soluble organic polymer, such as a copolymer of acrylate and maleate.

Les revĆŖtements proposĆ©s dans ces documents pour enrober les tablettes dĆ©tergentes sont prĆ©vus pour augmenter la stabilitĆ© desdites tablettes en formant une couche qui vient mĆ©caniquement maintenir la composition dĆ©tergente compactĆ©e. Toutefois ils sont complexes Ć  mettre en oeuvre, peuvent venir dĆ©naturer l'action de la tablette dĆ©tergente ou rĆ©duire l'efficacitĆ© et/ou le dĆ©litement de la tablette dĆ©tergente.The coatings proposed in these documents for coating the detergent tablets are intended to increase the stability of said tablets by forming a layer which mechanically maintains the compacted detergent composition. However they are complex to implement, may denature the action of the detergent tablet or reduce the effectiveness and / or disintegration of the detergent tablet.

Un but de la prĆ©sente invention est de proposer une tablette dĆ©tergente, notamment pour application lave-vaisselle, ayant une efficacitĆ© amĆ©liorĆ©e, une rĆ©sistance mĆ©canique et une stabilitĆ© permettant Ć  la tablette de pouvoir ĆŖtre manutentionnĆ©e et stockĆ©e sans subir de dĆ©gradation.An object of the present invention is to provide a detergent tablet, especially for dishwasher application, having improved efficiency, mechanical strength and stability allowing the tablet to be handled and stored without undergoing degradation.

Un but de la prƩsente invention est Ʃgalement de proposer une tablette dƩtergente, notamment pour application lave-vaisselle, prƩsentant une action amƩliorƩe tout en ayant un procƩdƩ de fabrication simple Ơ mettre en oeuvre.An object of the present invention is also to provide a detergent tablet, especially for dishwashing application, having an improved action while having a manufacturing method simple to implement.

EXPOSE DE L'INVENTIONSUMMARY OF THE INVENTION

A cette fin, on propose une tablette dĆ©tergente comprenant un corps formĆ© Ć  partir de poudre compactĆ©e, ledit corps Ć©tant enrobĆ© d'un revĆŖtement hydrosoluble, ledit revĆŖtement hydrosoluble ayant une composition comprenant un agent filmogĆØne et de l'eau, caractĆ©risĆ© en ce que la composition du revĆŖtement hydrosoluble comprend en outre au moins un agent spĆ©cifique pour amĆ©liorer l'efficacitĆ© de rinƧage de la tablette dĆ©tergente.To this end, there is provided a detergent tablet comprising a body formed from compacted powder, said body being coated with a water-soluble coating, said water-soluble coating having a composition comprising a film-forming agent and water, characterized in that the The composition of the water-soluble coating further comprises at least one specific agent to improve the rinsing efficacy of the detergent tablet.

Des aspects prƩfƩrƩs mais non limitatifs de cette tablette dƩtergente, pris seuls ou en combinaison, sont les suivants :

  • le revĆŖtement hydrosoluble a une Ć©paisseur comprise entre 1 Āµm et 1000 Āµm, de prĆ©fĆ©rence comprise entre 5 Āµm et 300 Āµm, et de prĆ©fĆ©rence encore comprise entre 15 Āµm et 150 Āµm.
  • le revĆŖtement hydrosoluble a une masse reprĆ©sentant entre 0,5% Ć  15% en masse par rapport au poids total de la tablette dĆ©tergente, de prĆ©fĆ©rence entre 2% Ć  5% en masse par rapport au poids total de la tablette dĆ©tergente.
  • l'agent spĆ©cifique permettant d'amĆ©liorer l'efficacitĆ© de rinƧage est un agent anti-spotting et/ou anti-filming.
  • l'au moins un agent spĆ©cifique est dans une proportion comprise entre 0.05% et 50% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble, de prĆ©fĆ©rence entre 2% et 20% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble.
  • l'au moins un agent spĆ©cifique est un polymĆØre.
  • l'au moins un agent spĆ©cifique est choisi parmi les copolymĆØres acrylique/styrĆØne modifiĆ©s hydrophobes, ou leurs combinaisons.
  • l'au moins un agent spĆ©cifique est choisi parmi les copolymĆØres d'acide acrylique et de monomĆØre sulfonĆ©, les copolymĆØres d'acide acrylique et d'acide sulfonique, les copolymĆØres d'acide acrylique et d'acide malĆ©ique, ou leurs combinaisons.
  • l'au moins un agent spĆ©cifique est choisi parmi les polymĆØres carboxylate, les polymĆØres carboxylate modifiĆ©s hydrophobes, en particulier les polymĆØres HASE, et leurs combinaisons.
  • l'agent filmogĆØne est dans une proportion comprise entre 5% et 80% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble, de prĆ©fĆ©rence comprise entre 20% et 60% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble, et de prĆ©fĆ©rence encore comprise entre 30% et 55% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble.
  • l'agent filmogĆØne est choisi parmi les alcools polyvinyliques, de prĆ©fĆ©rence parmi les alcools polyvinyliques ayant un taux d'hydrolyse avec un pourcentage molaire supĆ©rieur ou Ć©gal Ć  40%, de prĆ©fĆ©rence compris entre 70% et 98%, et de prĆ©fĆ©rence encore compris entre 80% et 90%.
  • l'agent filmogĆØne est choisi parmi les alcools polyvinyliques ayant une masse molaire en masse comprise entre 10000 g/mol et 200000 g/mol, et de prĆ©fĆ©rence comprise entre 15000 g/mol et 100000 g/mol.
  • la composition du revĆŖtement hydrosoluble comprend en outre un agent humectant.
  • l'agent humectant est dans une proportion infĆ©rieure ou Ć©gale Ć  25% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble, de prĆ©fĆ©rence dans une proportion comprise entre 1% et 20% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble, de prĆ©fĆ©rence encore dans une proportion comprise entre 2% et 10% en masse par rapport au poids total de la composition du revĆŖtement hydrosoluble.
  • l'agent humectant est choisi parmi la glycĆ©rine, les polyĆ©thylĆØnes glycol, et leurs combinaisons.
  • l'agent humectant est choisi parmi les polyĆ©thylĆØnes glycol ayant une masse molaire en masse comprise entre 1000 g/mol et 4000 g/mol.
Preferred but non-limiting aspects of this detergent tablet, taken alone or in combination, are as follows:
  • the water-soluble coating has a thickness of between 1 Ī¼m and 1000 Ī¼m, preferably between 5 Ī¼m and 300 Ī¼m, and more preferably between 15 Ī¼m and 150 Ī¼m.
  • the water-soluble coating has a mass representing between 0.5% and 15% by weight relative to the total weight of the detergent tablet, preferably between 2% and 5% by weight relative to the total weight of the detergent tablet.
  • the specific agent for improving the rinsing efficiency is an anti-spotting and / or anti-filming agent.
  • the at least one specific agent is in a proportion of between 0.05% and 50% by weight relative to the total weight of the composition of the water-soluble coating, preferably between 2% and 20% by weight relative to the total weight of the composition water-soluble coating.
  • the at least one specific agent is a polymer.
  • the at least one specific agent is selected from hydrophobic modified acrylic / styrene copolymers, or combinations thereof.
  • the at least one specific agent is selected from copolymers of acrylic acid and sulfonated monomer, copolymers of acrylic acid and sulfonic acid, copolymers of acrylic acid and maleic acid, or combinations thereof.
  • the at least one specific agent is chosen from carboxylate polymers, hydrophobic modified carboxylate polymers, in particular HASE polymers, and combinations thereof.
  • the film-forming agent is in a proportion of between 5% and 80% by weight relative to the total weight of the composition of the water-soluble coating, preferably between 20% and 60% by weight relative to the total weight of the coating composition water-soluble, and more preferably between 30% and 55% by weight relative to the total weight of the composition of the water-soluble coating.
  • the film-forming agent is chosen from polyvinyl alcohols, preferably from polyvinyl alcohols having a degree of hydrolysis with a molar percentage greater than or equal to 40%, preferably of between 70% and 98%, and more preferably between 80% and 90%.
  • the film-forming agent is chosen from polyvinyl alcohols having a molar mass of between 10,000 g / mol and 200,000 g / mol, and preferably of between 15,000 g / mol and 100,000 g / mol.
  • the composition of the water-soluble coating further comprises a humectant.
  • the humectant is in a proportion less than or equal to 25% by weight relative to the total weight of the composition of the water-soluble coating, preferably in a proportion of between 1% and 20% by weight relative to the total weight of the composition water-soluble coating, preferably in a proportion of between 2% and 10% by weight relative to the total weight of the composition of the water-soluble coating.
  • the humectant is selected from glycerine, polyethylene glycol, and combinations thereof.
  • the humectant is chosen from polyethylene glycols having a molar mass of between 1000 g / mol and 4000 g / mol.

DESCRIPTION DETAILLEE DE L'INVENTIONDETAILED DESCRIPTION OF THE INVENTION

On propose donc un produit dĆ©tergent sous forme de tablette enrobĆ© d'un revĆŖtement, Ć©galement appelĆ© coating, formĆ©e d'une solution hydrosoluble, permettant de recouvrir la surface de la tablette en formant un film homogĆØne adhĆ©rant Ć  la surface de la tablette. Le produit dĆ©tergent sous forme de tablette peut par exemple ĆŖtre un dĆ©tergent lave-vaisselle.A detergent product is therefore proposed in the form of a coated tablet, also called a coating, formed of a water-soluble solution, making it possible to cover the surface of the tablet by forming a homogeneous film adhering to the surface of the tablet. The detergent product in tablet form may for example be a dishwashing detergent.

La tablette dĆ©tergente proposĆ©e comprend un corps formĆ© par exemple Ć  partir de poudre compactĆ©e, ledit corps Ć©tant enrobĆ© d'un revĆŖtement hydrosoluble. Le revĆŖtement hydrosoluble utilisĆ© a une composition comprenant un agent filmogĆØne et de l'eau, et prĆ©sente la particularitĆ© de comprendre en outre au moins un agent spĆ©cifique pour amĆ©liorer l'efficacitĆ© de rinƧage de la tablette dĆ©tergente. Comme on le verra plus loin, la composition du revĆŖtement hydrosoluble peut aussi comprendre un agent humectant.The detergent tablet proposed comprises a body formed for example from compacted powder, said body being coated with a water-soluble coating. The water-soluble coating used has a composition comprising a film-forming agent and water, and has the particularity of further comprising at least one specific agent to improve the rinsing efficiency of the detergent tablet. As will be seen below, the composition of the water-soluble coating may also comprise a humectant.

L'agent spĆ©cifique utilisĆ© pour amĆ©liorer l'efficacitĆ© de rinƧage de la tablette dĆ©tergente est de prĆ©fĆ©rence choisi parmi les composĆ©s ayant une action Ā« anti-spotting Ā» (que l'on pourrait Ć©galement qualifier d'action anti-trace) et/ou une action Ā« anti-filming Ā» (que l'on pourrait Ć©galement qualifier d'action anti-film).The specific agent used to improve the rinsing efficacy of the detergent tablet is preferably selected from compounds having an "anti-spotting" action (which could also be described as anti-trace action) and / or action "anti-filming" (which could also be called anti-film action).

Par Ā« spotting Ā», on entend toute trace sur un Ć©lĆ©ment de vaisselle, causĆ©e par le sĆ©chage des gouttes d'eau sur la surface du matĆ©riau formant l'Ć©lĆ©ment de vaisselle, en particulier le verre. Le calcium et le magnĆ©sium prĆ©sents dans l'eau peuvent par exemple se dĆ©poser sur la surface du verre et former des traces lors du sĆ©chage en lave-vaisselle. Plus l'eau prĆ©sente une duretĆ© importante plus elle contient une quantitĆ© importante d'ions calcium et magnĆ©sium.By "spotting" is meant any trace on a dishware element, caused by the drying of drops of water on the surface of the material forming the dishware, in particular glass. Calcium and magnesium present in water can for example be deposited on the surface of the glass and form traces during drying in the dishwasher. The higher the water hardness, the higher the amount of calcium and magnesium ions it contains.

Par Ā« filming Ā», on entend toute apparition d'un film/dĆ©pĆ“t blanc sur la totalitĆ© ou une grande partie de la surface du matĆ©riau formant l'Ć©lĆ©ment de vaisselle, en particulier l'opacification du verre. Les ions calcium et magnĆ©sium prĆ©sents dans l'eau peuvent par exemple former des dĆ©pĆ“ts de calcaire plus ou moins uniforme Ć  la surface du verre."Filming" means any appearance of a film / white deposit on all or a large part of the surface of the material forming the dishware, in particular the opacification of the glass. The calcium and magnesium ions present in the water can for example form deposits of limestone more or less uniform on the surface of the glass.

Comme on le verra plus loin dans cette description, l'utilisation d'un agent spĆ©cifique prĆ©vu pour amĆ©liorer l'efficacitĆ© de rinƧage de la tablette dĆ©tergente, tel qu'un agent anti-spotting et/ou anti-filming, dans la composition formant le revĆŖtement enrobant la tablette dĆ©tergente, permet d'avoir une stabilitĆ© accrue par rapport aux tablettes enrobĆ©es existantes.As will be seen later in this description, the use of a specific agent intended to improve the rinsing efficiency of the detergent tablet, such as an anti-spotting and / or anti-filming agent, in the composition forming the coating coating the detergent tablet, allows for increased stability over existing coated tablets.

PrĆ©voir un tel agent spĆ©cifique dans la composition formant le revĆŖtement enrobant la tablette dĆ©tergente est Ć©galement particuliĆØrement avantageux puisqu'il permet d'utiliser notamment des agents Ć©tant gĆ©nĆ©ralement sous forme liquide et qui sont donc difficilement utilisables dans les formules dĆ©tergentes en tablette. En effet, des agents spĆ©cifiques sous forme liquide sont gĆ©nĆ©ralement difficiles Ć  introduire dans le mĆ©lange pulvĆ©rulent destinĆ© Ć  ĆŖtre compactĆ©, et entrainent en outre des problĆØmes de stabilitĆ© de la tablette compactĆ©e finale, en particulier Ć  cause de l'eau prĆ©sente dans de tels agents spĆ©cifiques sous forme liquide qui peut rĆ©agir avec les autres matiĆØres premiĆØres de la formule dĆ©tergente.Providing such a specific agent in the composition forming the coating coating the detergent tablet is also particularly advantageous since it makes it possible to use in particular agents generally being in liquid form and which are therefore difficult to use in tablet detergent formulations. Indeed, specific agents in liquid form are generally difficult to introduce into the powder mixture to be compacted, and further cause problems of stability of the final compacted tablet, especially because of the water present in such agents specific in liquid form that can react with other raw materials of the detergent formula.

Produit dƩtergent sous forme tabletteDetergent product in tablet form

Le produit dĆ©tergent utilisĆ© est de prĆ©fĆ©rence sous la forme d'une tablette qui prĆ©sente une cohĆ©sion suffisante pour pouvoir ĆŖtre manipulĆ©e sans ĆŖtre cassĆ©e et qui se dĆ©sintĆØgre facilement dans l'eau.The detergent product used is preferably in the form of a tablet which has sufficient cohesion to be handled without being broken and which easily disintegrates in water.

La tablette ne nĆ©cessite pas d'avoir une duretĆ© Ć©levĆ©e, sa cohĆ©sion et rĆ©sistance mĆ©canique Ć©tant notamment renforcĆ©es par l'utilisation d'un revĆŖtement venant enrober la tablette, c'est-Ć -dire adhĆ©rer Ć  la surface de la tablette.The tablet does not require a high hardness, its cohesion and mechanical strength being enhanced by the use of a coating coming to coat the tablet, that is to say adhere to the surface of the tablet.

La tablette prĆ©sente un corps formĆ© par compaction par exemple, notamment Ć  partir d'un mĆ©lange de matiĆØres premiĆØres sous forme de poudre ou de granulĆ©, mais Ć©galement sous forme liquide.The tablet has a body formed by compaction for example, in particular from a mixture of raw materials in the form of powder or granules, but also in liquid form.

Les tablettes dĆ©tergentes sont constituĆ©es d'un mĆ©lange de composants comprenant des actions diffĆ©rentes, ces composants pouvant par exemple ĆŖtre choisis parmi des tensio-actifs, charges, sĆ©questrants, agents de blanchiment, enzymes, activateurs de blanchiment, agents alcalins, polymĆØres, parfums, colorants.The detergent tablets consist of a mixture of components comprising different actions, these components may for example be chosen from surfactants, fillers, sequestering agents, bleaching agents, enzymes, bleaching activators, alkaline agents, polymers, perfumes, dyes.

La tablette dĆ©tergente peut ĆŖtre constituĆ©e d'une unique couche ou d'un empilement de plusieurs couches qui sont superposĆ©es les unes sur les autres, formant ainsi un bloc uniforme et compact. Pour une tablette multicouche, les diffĆ©rentes couches peuvent avoir une composition identique ou diffĆ©rente.The detergent tablet may consist of a single layer or a stack of several layers that are superimposed on each other, forming a uniform and compact block. For a multilayer tablet, the different layers may have the same or different composition.

La tablette a de prƩfƩrence une forme allongƩe avec une section ayant une forme quelconque, par exemple circulaire, ovale, octogonale, ou parallƩlƩpipƩdique.The tablet preferably has an elongated shape with a section having any shape, for example circular, oval, octagonal, or parallelepipedal.

Lorsque la section de la tablette est parallĆ©lĆ©pipĆ©dique, typiquement carrĆ©e ou rectangulaire, les coins de la tablette peuvent ĆŖtre courbes de maniĆØre Ć  ce qu'ils soient moins cassants.When the section of the tablet is parallelepiped, typically square or rectangular, the corners of the tablet can be curved so that they are less brittle.

Chaque couche a de prĆ©fĆ©rence la mĆŖme section de sorte que l'empilement de couches forme une tablette uniforme.Each layer preferably has the same section so that the stack of layers forms a uniform tablet.

La tablette dƩtergente a de prƩfƩrence une masse comprise entre 1 gramme et 100 grammes, et de prƩfƩrence encore comprise entre 5 grammes et 60 grammes.The detergent tablet preferably has a mass of between 1 gram and 100 grams, and more preferably between 5 grams and 60 grams.

La tablette prƩsente de prƩfƩrence une rƩsistance mƩcanique comprise entre 5 Newtons et 300 Newtons, et de prƩfƩrence encore entre 10 Newtons et 90 Newtons.The tablet preferably has a mechanical strength of between 5 Newtons and 300 Newtons, and more preferably between 10 Newtons and 90 Newtons.

Pour former une tablette multicouches, le processus de fabrication utilisĆ© consiste gĆ©nĆ©ralement Ć  former progressivement un complexe de plusieurs couches et Ć  compacter ce complexe Ć  chaque nouvel ajout de couche de maniĆØre Ć  solidifier la tablette. Les tablettes sont fabriquĆ©es par compression directe avec une presse hydraulique ou une presse rotative, notamment lorsque l'on souhaite former des tablettes Ć  une cadence industrielle.To form a multilayer tablet, the manufacturing process used generally consists of progressively forming a complex of several layers and compacting this complex with each new addition of layer so as to solidify the tablet. The tablets are manufactured by direct compression with a hydraulic press or a rotary press, especially when it is desired to form tablets at an industrial rate.

La premiĆØre Ć©tape consiste donc Ć  mĆ©langer les composants destinĆ©s pour former les compositions correspondant Ć  chacune des couches. Le mĆ©lange correspondant Ć  la premiĆØre couche est introduit dans la matrice puis prĆ©-compactĆ© pour former la premiĆØre couche. Le mĆ©lange de la deuxiĆØme couche est ensuite introduit dans la matrice sur la premiĆØre couche puis prĆ©-compactĆ© comme pour la premiĆØre couche, de la mĆŖme maniĆØre les autres couches de la tablette sont introduites dans la matrice. L'ensemble des couches est ensuite compactĆ© pour obtenir une tablette rĆ©sistante aux chocs.The first step is therefore to mix the components intended to form the compositions corresponding to each of the layers. The mixture corresponding to the first layer is introduced into the matrix and then pre-compacted to form the first layer. The mixture of the second layer is then introduced into the matrix on the first layer and then pre-compacted as for the first layer, in the same way the other layers of the tablet are introduced into the matrix. The set of layers is then compacted to obtain a shock-resistant tablet.

Les forces de prƩ-compaction utilisƩes sont de prƩfƩrence comprises entre 0 kN et 100 kN (kilonewtons), et de prƩfƩrence encore entre 0 kN et 50 kN. La force de compression utilisƩe pour la compaction finale est de prƩfƩrence comprise entre 5 kN et 200 kN, et de prƩfƩrence encore entre 10 kN et 100 kN.The pre-compaction forces used are preferably between 0 kN and 100 kN (kilonewtons), and more preferably between 0 kN and 50 kN. The compression force used for the final compaction is preferably between 5 kN and 200 kN, and more preferably between 10 kN and 100 kN.

Une tablette dƩtergente pour lave-vaisselle comprend une combinaison d'un ou plusieurs des composants dƩcrits plus en dƩtail ci-dessous, sans que ce ne soit limitatif.A dishwasher detergent tablet includes a combination of one or more of the components described in more detail below, without being limiting thereto.

Enzymesenzymes

Pour permettre la dĆ©gradation des salissures prĆ©sentes sur la vaisselle, la tablette contient de prĆ©fĆ©rence des enzymes afin de former un systĆØme enzymatique. Ces enzymes sont par exemple choisies parmi les protĆ©ases, les amylases, les lipases, et leurs combinaisons.To allow the degradation of the soil on the dishes, the tablet preferably contains enzymes to form an enzymatic system. These enzymes are for example chosen from proteases, amylases, lipases, and combinations thereof.

Ces enzymes se prƩsentent gƩnƩralement sous la forme de granulƩs qui contiennent une certaine quantitƩ d'enzymes actives.These enzymes are generally in the form of granules that contain a certain amount of active enzymes.

Les tablettes dƩtergentes que l'on utilise prƩfƩrentiellement ont une composition globale intƩgrant des enzymes dont la quantitƩ totale d'enzymes actives est comprise entre 0,003% et 5% en masse, et de prƩfƩrence entre 0,003% et 2% en masse.The detergent tablets that are preferably used have an overall composition integrating enzymes whose total amount of active enzymes is between 0.003% and 5% by weight, and preferably between 0.003% and 2% by weight.

On peut utiliser les amylases pour dĆ©composer les tĆ¢ches Ć  base d'amidon, tels que par exemple le produit distribuĆ© par la sociĆ©tĆ© Genencor sous la rĆ©fĆ©rence Ā« Powerase 16000HS Ā».Amylases can be used to decompose starch-based stains, such as, for example, the product dispensed by Genencor under the reference "Powerase 16000HS".

La tablette peut Ć©galement contenir des protĆ©ases pour agir sur les tĆ¢ches protĆ©iniques telle que la viande et les oeufs. On peut par exemple utiliser le produit rĆ©fĆ©rencĆ© Ā« Excellase 2250D Ā» distribuĆ© par la sociĆ©tĆ© Genencor.The tablet may also contain proteases to act on protein tasks such as meat and eggs. One can for example use the product referenced "Excellase 2250D" distributed by the company Genencor.

La tablette peut Ć©galement contenir des lipases afin d'amĆ©liorer la dĆ©gradation des tĆ¢ches de graisse prĆ©sentent sur la vaisselle.The tablet may also contain lipases to improve the breakdown of grease stains on the dishes.

Agent de blanchiments et activateurs d'agent de blanchimentBleaching agent and bleach activators

Pour permettre la dĆ©gradation des tĆ¢ches oxydables tel que le thĆ©, le cafĆ©, le vin rouge, la tablette contient de prĆ©fĆ©rence un agent de blanchiment, c'est Ć  dire une substance capable d'oxyder directement ou indirectement les composĆ©s organiques dĆ©crits.To allow the degradation of oxidizable stains such as tea, coffee, red wine, the tablet preferably contains a bleaching agent, that is to say a substance capable of directly or indirectly oxidizing the organic compounds described.

Les agents de blanchiment pourront ĆŖtre du type perborate de sodium mono ou tĆ©trahydratĆ©, percarbonate de sodium, persilicate de sodium, et persulfate de sodium.The bleaching agents may be of the sodium perborate mono or tetrahydrate type, sodium percarbonate, sodium persilicate, and sodium persulfate.

En milieu alcalin, ces composĆ©s libĆØrent du peroxyde d'hydrogĆØne au contact de l'eau gĆ©nĆ©rant ainsi une source d'oxygĆØne actif.In alkaline medium, these compounds release hydrogen peroxide in contact with water, thus generating a source of active oxygen.

La tablette comprend de prƩfƩrence entre 1% et 50% en masse d'agent de blanchiment, et de prƩfƩrence encore entre 5% et 20% en masse.The tablet preferably comprises between 1% and 50% by weight of bleaching agent, and more preferably between 5% and 20% by weight.

Pour permettre un blanchiment de la vaisselle encore plus efficace, la tablette contient de prĆ©fĆ©rence un activateur de l'agent de blanchiment du type tĆ©traacĆ©thylĆØnediamine (TAED), pentaacĆ©tylglucose (PAG), tĆ©traacĆ©thylglycoluryl (TAGU) et benzoloxybenzene sulfonate de sodium.To provide even more effective dish washing, the tablet preferably contains a tetraacetylenediamine (TAED), pentaacetylglucose (PAG), tetraacethylglycoluryl (TAGU) and sodium benzoloxybenzene sulfonate bleach activator.

Ces activateurs rĆ©agissent dans le bain de lavage avec le peroxyde d'hydrogĆØne, donnant des composĆ©s chimiques dont la performance sur les salissures organiques est supĆ©rieure, notamment pour des raisons d'affinitĆ© chimique.These activators react in the wash bath with hydrogen peroxide, giving chemical compounds whose performance on organic soils is higher, especially for reasons of chemical affinity.

La tablette comprend de prƩfƩrence entre 0,5% et 40% en masse d'activateur de l'agent de blanchiment, et de prƩfƩrence encore entre 1% et 10% en masse.The tablet preferably comprises between 0.5% and 40% by weight activator of the bleaching agent, and more preferably between 1% and 10% by weight.

De maniĆØre prĆ©fĆ©rĆ©e, la tablette comprend un ratio entre agents de blanchiment et activateurs d'agents de blanchiment correspondant Ć  un ratio molaire de 6 pour 1, de prĆ©fĆ©rence encore un ratio molaire de 5 pour 1.Preferably, the tablet comprises a ratio between bleaching agents and bleach activators corresponding to a molar ratio of 6 to 1, more preferably a molar ratio of 5 to 1.

La tablette peut Ć©galement contenir des catalyseurs permettant d'amĆ©liorer l'efficacitĆ© des agents sur les taches oxydables. On peut citer par exemple les catalyseurs au manganĆØse tel que le produit rĆ©fĆ©rencĆ© Ā« Peractive FDO X Ā» commercialisĆ© par la sociĆ©tĆ© Weylchem.The tablet may also contain catalysts to improve the effectiveness of agents on oxidizable stains. Mention may be made, for example, of manganese catalysts such as the product referred to as "Peractive FDO X" marketed by Weylchem.

Adjuvants de dƩtergence/sƩquestrants (ou builders) Detergents / sequestrants (or builders)

L'efficacitĆ© du lavage sera augmentĆ©e si la tablette comprend en outre des adjuvants de dĆ©tergence, que l'on appelle Ć©galement Ā« builders Ā».The effectiveness of the washing will be increased if the tablet further comprises detergency builders, also called "builders".

Les adjuvants de dĆ©tergence piĆØgent les ions mĆ©talliques tel que le calcium et le magnĆ©sium prĆ©sents dans la solution de lavage par complexation, Ć©change d'ion ou prĆ©cipitation.Detergent additives trap metal ions such as calcium and magnesium present in the wash solution by complexation, ion exchange or precipitation.

Les adjuvants de dƩtergence sont prƩfƩrentiellement prƩsents Ơ hauteur de 5% Ơ 99% en masse, et de prƩfƩrence encore de 10% Ơ 50% en masse.Detergent adjuvants are preferably present in an amount of from 5% to 99% by weight, and more preferably from 10% to 50% by weight.

Les adjuvants de dĆ©tergence hydrosolubles non phosphorĆ©s peuvent ĆŖtre organiques ou inorganiques.Non-phosphorus water soluble builders can be organic or inorganic.

Les composĆ©s inorganiques qui peuvent ĆŖtre prĆ©sents sont choisis parmi les zĆ©olithes, les phyllosilicates, les carbonates de mĆ©tal alcalin (gĆ©nĆ©ralement de sodium), et les silicates de sodium, des mĆ©langes de carbonate de sodium et de silicates de sodium comme le produit rĆ©fĆ©rencĆ© Ā« questlock Ā» distribuĆ© par la sociĆ©tĆ© Amcol.The inorganic compounds that may be present are chosen from zeolites, phyllosilicates, alkali metal carbonates (generally sodium), and sodium silicates, mixtures of sodium carbonate and sodium silicates, such as the product referenced "questlock Distributed by the company Amcol.

Les composĆ©s organiques qui peuvent ĆŖtre prĆ©sents sont choisis parmi les polymĆØres de polycarboxylate tels que les polyacrylates, les copolymĆØres acrylique/malĆ©ique et les phosphonates acryliques, les polycarboxylates monomĆØres tels que les citrates, les gluconates, les oxydisuccinates, les mono-, di- et tri-succinates de glycĆ©rol, les carboxymĆ©thyloxysuccinates, les composĆ©s amino polycarboxyliques tels que les carboxymĆ©thyloxymalonates d'acide mĆ©thylglycinediacĆ©tate (MGDA), acide diacĆ©tique glutamique (GLDA), l'imminodisuccinate (IDS), Ć©thylĆØnediamine disuccinate (EDDS), les dipicolinates, les nitrilotriacĆ©tates et les hydroxyĆ©thyliminodi acĆ©tates.The organic compounds that may be present are chosen from polycarboxylate polymers such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, mono-, di- and glycerol tri-succinates, carboxymethyloxysuccinates, polycarboxylic amino compounds such as methylglycinediacetate (MGDA) carboxymethyloxymalonates, glutamic diacetic acid (GLDA), imminodisuccinate (IDS), ethylenediamine disuccinate (EDDS), dipicolinates, nitrilotriacetates and hydroxyethyliminodi acetates.

Le citrate de sodium et l'acide mĆ©thylglycinediacetate (MGDA) sont des adjuvants de dĆ©tergence particuliĆØrement prĆ©fĆ©rĆ©s pour les tablettes de lave-vaisselle.Sodium citrate and methylglycinediacetate acid (MGDA) are particularly preferred detergency builders for dishwasher tablets.

La classe d'adjuvants hydrosolubles phosphorƩs comprend les orthophosphates, les mƩta-phosphates, les pyrophosphates et les polyphosphates de mƩtal alcalin.The class of water-soluble phosphorus adjuvants includes orthophosphates, methaphosphates, pyrophosphates and alkali metal polyphosphates.

Des exemples spƩcifiques d'adjuvants de dƩtergence phosphorƩs inorganiques comprennent les tripolyphosphates, les orthophosphates et les hexamƩtaphosphates de sodium et potassium.Specific examples of inorganic phosphorus detergency builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.

Le tripolyphosphate de sodium est un adjuvant phosphorĆ© particuliĆØrement prĆ©fĆ©rĆ© pour les tablettes lave-vaisselle. Il existe sous forme hydratĆ©e, anhydre ou partiellement hydratĆ©e, et on peut utiliser des mĆ©langes de ces formes pour rĆ©guler la vitesse de dĆ©sintĆ©gration et la dissolution de la tablette.Sodium tripolyphosphate is a particularly preferred phosphorus adjuvant for dishwasher tablets. It exists in hydrated, anhydrous or partially hydrated form, and mixtures of these forms can be used to regulate the rate of disintegration and dissolution of the tablet.

Pour permettre un lavage efficace de la vaisselle, le pH de la solution de lavage doit ĆŖtre au moins de 9 et de prĆ©fĆ©rence compris entre 9,5 et 12,5. La plupart des adjuvants de dĆ©tergence sont alcalins, de sorte qu'il ne soit pas nĆ©cessaire d'ajouter d'autres composĆ©s Ć  la tablette pour ajuster le pH.To allow efficient washing of the dishes, the pH of the wash solution must be at least 9 and preferably between 9.5 and 12.5. Most detergency builders are alkaline, so there is no need to add other compounds to the tablet to adjust the pH.

Tensioactifssurfactants

Pour un lavage efficace, la tablette contient de prƩfƩrence un ou plusieurs tensioactifs non ioniques, par exemple des tensioactifs non ioniques faiblement moussant. Les tensioactifs sont des molƩcules amphiphiles, qui sont composƩes d'une partie lipophile apolaire et d'une partie hydrophile polaire.For efficient washing, the tablet preferably contains one or more nonionic surfactants, for example low foaming nonionic surfactants. The surfactants are amphiphilic molecules, which are composed of an apolar lipophilic part and a polar hydrophilic part.

Pour les tablettes dƩtergentes pour lave-vaisselle, la quantitƩ de tensioactifs dans la tablette est de prƩfƩrence comprise entre 0,05% et 20% en masse, et de prƩfƩrence encore entre 1% et 5% en masse.For detergent tablets for dishwashers, the amount of surfactants in the tablet is preferably in the range of 0.05% to 20% by weight, and more preferably in the range of 1% to 5% by weight.

Les tensioactifs sous forme solide sont plus faciles Ć  utiliser dans les tablettes qui ont Ć©galement des compositions solides. Cependant, lorsque le tensioactif est sous forme liquide, il peut Ć©galement ĆŖtre introduit dans la tablette, auquel cas il est adsorbĆ© sur des supports tels que le carbonate de sodium ou la silice.Surfactants in solid form are easier to use in tablets which also have solid compositions. However, when the surfactant is in liquid form, it can also be introduced into the tablet, in which case it is adsorbed on supports such as sodium carbonate or silica.

Les tensioactifs non ioniques de synthĆØse peuvent ĆŖtre gĆ©nĆ©ralement dĆ©finis comme des composĆ©s issus de la condensation entre des groupements d'oxyde d'alkylĆØne et des composĆ©s organiques hydrophobes, pouvant ĆŖtre aliphatiques ou aromatiques. La longueur de la partie hydrophile du tensioactif peut ĆŖtre facilement ajustĆ©e afin d'obtenir un composĆ© soluble dans l'eau ayant le HLB dĆ©sirĆ©, le HLB traduisant le degrĆ© d'hydrophilie ou de lipophilie du tensioactif.The synthetic nonionic surfactants may be generally defined as compounds derived from the condensation between alkylene oxide groups and hydrophobic organic compounds, which may be aliphatic or aromatic. The length of the hydrophilic portion of the surfactant can be easily adjusted to obtain a water-soluble compound having the desired HLB, the HLB translating the degree of hydrophilicity or lipophilicity of the surfactant.

La liste non exhaustive des tensioactifs non ioniques qui peuvent ĆŖtre utilisĆ©s dans la tablette regroupe les alcools gras ethoxylĆ©s et/ou propoxylĆ©s, copolymĆØre d'oxyde d'Ć©thylĆØne et d'oxyde de propylĆØne, et les alkyl polyglucoside, alcool gras polyglycolĆ©ther modifiĆ©.The non-exhaustive list of nonionic surfactants that can be used in the tablet includes ethoxylated and / or propoxylated fatty alcohols, copolymer of ethylene oxide and propylene oxide, and alkyl polyglucoside, modified polyglycol ether alcohol.

Il est Ʃgalement possible d'utiliser des tensioactifs anioniques, pour notamment amƩliorer le sƩchage de la vaisselle pour les tablettes lave-vaisselle. Dans ce cas, la quantitƩ de tensioactifs anioniques prƩsents dans la tablette est de prƩfƩrence comprise entre 0,05% et 40% en masse, et de prƩfƩrence entre 1% et 20% en masse.It is also possible to use anionic surfactants, especially to improve the drying of dishes for dishwasher tablets. In this case, the amount of anionic surfactants present in the tablet is preferably between 0.05% and 40% by weight, and preferably between 1% and 20% by weight.

La liste non exhaustive des tensioactifs anioniques qui peuvent ĆŖtre utilisĆ©s dans les tablettes dĆ©tergentes regroupe les alkylbenzĆØnesulfonates, paraffin-ou alcanesulfonates, alcool sulfates primaires, Ī±-olefinsulfonates, alkyl ether sulfates, sulfosuccinates, acyl isethionates, methyl ester sulfonates, savon, sulfoalkylamides d'acides gras, diglycolamide sulfates, N-acyl amino acides, et alkyl polyoxyĆ©thylĆØne carboxylates.The non-exhaustive list of anionic surfactants that can be used in detergent tablets includes alkylbenzene sulfonates, paraffin-or alkanesulfonates, primary alcohol sulfates, Ī±-olefinsulfonates, alkyl ether sulfates, sulfosuccinates, acyl isethionates, methyl ester sulfonates, soap, sulfoalkylamides. fatty acids, diglycolamide sulfates, N-acyl amino acids, and alkyl polyoxyethylene carboxylates.

Composants complƩmentairesComplementary components

Outre ces composants de base de la tablette dƩtergente, celle-ci peut comprendre des composants complƩmentaires qui seront utilisƩs selon les spƩcificitƩs dƩsirƩes de la tablette dƩtergente.In addition to these basic components of the detergent tablet, this may include additional components that will be used according to the desired specificities of the detergent tablet.

On peut par exemple utiliser des additifs de protection, comme par exemple le benzotriazole et les sels de zinc. Ces additifs forment un systĆØme de protection de la vaisselle et du lave-vaisselle contre les attaques chimiques non dĆ©sirĆ©es en provenance de l'un et l'autre des composants de la tablette.For example, protective additives such as benzotriazole and zinc salts may be used. These additives form a dishwashing and dishwasher protection system against unwanted chemical attack from either component of the tablet.

Des agents chĆ©latants destinĆ©s Ć  piĆ©ger les ions mĆ©talliques peuvent Ć©galement ĆŖtre prĆ©sents dans la composition. On les appelle aussi agents sĆ©questrants ou complexant d'ions mĆ©talliques. Le cas Ć©chĆ©ant, il est prĆ©fĆ©rable que la quantitĆ© d'agents chĆ©latants soit de l'ordre de 0,5% Ć  20% en masse, et de prĆ©fĆ©rence de 0,5% Ć  5% en masse. Les agents chĆ©latants prĆ©fĆ©rĆ©s comprennent les phosphonates organiques, amino-carboxylates, les composĆ©s substituĆ©s de maniĆØre polyfonctionnelle et leurs mĆ©langes. On peut Ć©galement utiliser les homopolymĆØres d'acide acrylique ou copolymĆØres d'acide acrylique et malĆ©iques.Chelating agents for trapping metal ions may also be present in the composition. They are also known as sequestering agents or complexing metal ions. If necessary, it is preferable that the amount of chelating agents is of the order of 0.5% to 20% by weight, and preferably 0.5% to 5% by weight. Preferred chelating agents include organic phosphonates, amino carboxylates, polyfunctionally substituted compounds, and mixtures thereof. It is also possible to use homopolymers of acrylic acid or copolymers of acrylic and maleic acid.

Il peut aussi ĆŖtre utilisĆ© des agents d'Ć©clatement, qui ont pour but d'accĆ©lĆ©rer le dĆ©litement de la couche dans laquelle ils sont incorporĆ©s. Les agents d'Ć©clatements prĆ©fĆ©rĆ©s comprennent les carboxymĆ©thylcellulose, les carboxymethylcellulose rĆ©ticulĆ©s, le sodium croscarmellose, la cellulose, le polyvinylpyrrolidone et leurs mĆ©langes.It can also be used bursting agents, which are intended to accelerate the disintegration of the layer in which they are incorporated. Preferred bursting agents include carboxymethylcellulose, crosslinked carboxymethylcellulose, croscarmellose sodium, cellulose, polyvinylpyrrolidone and mixtures thereof.

On peut aussi ajouter des colorants pour diffƩrencier les couches les unes par rapport aux autres. Ces colorants ont essentiellement pour objet d'amƩliorer l'aspect esthƩtique de la tablette vis-Ơ-vis du consommateur.Dyes can also be added to differentiate the layers from each other. These dyes are essentially intended to improve the aesthetic appearance of the tablet vis-Ơ-vis the consumer.

On peut aussi rajouter du parfum pour masquer les mauvaises odeurs lors de l'ouverture du lave-vaisselle.You can also add perfume to mask odors when opening the dishwasher.

On peut Ć©galement rajouter des additifs de pastillages tels que les liants qui permettent d'augmenter la duretĆ© de la pastille et de diminuer sa friabilitĆ©. Parmi les liants qui peuvent ĆŖtre utilisĆ©s, on peut citer notamment les polyĆ©thylĆØnes glycol.We can also add pastilles additives such as binders that can increase the hardness of the pellet and reduce its friability. Among the binders that can be used include polyethylene glycol.

Des lubrifiants peuvent Ć©galement ĆŖtre utilisĆ©s pour faciliter l'Ć©jection de la tablette Ć  la sortie de la presse rotative. Parmi les lubrifiants qui peuvent ĆŖtre utilisĆ©s, on peut citer les stĆ©arates de mĆ©tal alcalin comme le stĆ©arate de calcium et le stĆ©arate de magnĆ©sium.Lubricants can also be used to facilitate ejection of the tablet at the output of the rotary press. Among the lubricants that can be used include alkali metal stearates such as calcium stearate and magnesium stearate.

D'autres additifs pourraient ĆŖtre utilisĆ©s comme par exemple des agents anti-mousses.Other additives could be used such as anti-foaming agents.

RevĆŖtement hydrosoluble venant enrober le corps de la tablette dĆ©tergenteWater-soluble coating that coats the body of the detergent tablet

Une fois que le corps principal constituant la tablette dĆ©tergente est formĆ©, on utilise une solution particuliĆØre pour former le revĆŖtement hydrosoluble, ou coating, destinĆ© Ć  recouvrir la surface de la tablette.Once the main body constituting the detergent tablet is formed, a particular solution is used to form the water-soluble coating, or coating, intended to cover the surface of the tablet.

Comme on le verra plus loin dans les essais comparatifs, ce revĆŖtement venant enrober le corps de la tablette dĆ©tergente a d'autres avantages que celui de protĆ©ger le corps contre les chocs et contre l'humiditĆ© prĆ©sente dans l'air ambiant. En effet, il va permettre par exemple d'amĆ©liorer l'action de la tablette dĆ©tergente, notamment en ce qui concerne le rinƧage. Il va en outre participer Ć  la stabilitĆ© globale de la tablette dĆ©tergente tout en offrant un meilleur dĆ©litement et une faible friabilitĆ© du corps.As will be seen later in the comparative tests, this coating coming to coat the body of the detergent tablet has other advantages than that of protecting the body against shocks and against the humidity present in the ambient air. Indeed, he is going allow for example to improve the action of the detergent tablet, particularly with regard to rinsing. It will also participate in the overall stability of the detergent tablet while providing better disintegration and low friability of the body.

Comme indiquĆ© plus haut, la solution utilisĆ©e pour former le revĆŖtement hydrosoluble contient un agent filmogĆØne, de l'eau et un agent spĆ©cifique destinĆ© Ć  amĆ©liorer l'efficacitĆ© de rinƧage de la tablette dĆ©tergente.As indicated above, the solution used to form the water soluble coating contains a film forming agent, water and a specific agent to improve the rinsing efficiency of the detergent tablet.

En tant qu'agent filmogĆØne, la solution peut par exemple comprendre de l'alcool polyvinylique (PVA).As a film-forming agent, the solution may for example comprise polyvinyl alcohol (PVA).

Les PVA qui peuvent ĆŖtre utilisĆ©s ont de prĆ©fĆ©rence un taux d'hydrolyse supĆ©rieur ou Ć©gal Ć  40% (% molaire), de prĆ©fĆ©rence compris entre 70% et 98% (% molaires), et de prĆ©fĆ©rence encore un taux d'hydrolyse compris entre 80% et 90%.The PVAs that can be used preferably have a degree of hydrolysis greater than or equal to 40% (mol%), preferably between 70% and 98% (mol%), and more preferably a degree of hydrolysis between 80% and 90%.

Les PVA utilisƩs ont de prƩfƩrence une masse molaire en masse (Mw) comprise entre 10.000 g/mol et 200.000 g/mol, et de prƩfƩrence encore entre 15.000 g/mol et 100.000 g/mol. La masse molaire en masse du PVA impacte fortement la viscositƩ finale de la solution de coating.The PVAs used preferably have a molar mass (Mw) of between 10,000 g / mol and 200,000 g / mol, and more preferably between 15,000 g / mol and 100,000 g / mol. The mass molar mass of the PVA strongly impacts the final viscosity of the coating solution.

On pourra par exemple utiliser les PVA commercialisĆ©s sous la rĆ©fĆ©rence Ā« Mowiol Ā» par la sociĆ©tĆ© Clariant, comme plus particuliĆØrement les produits rĆ©fĆ©rencĆ©s Ā« Mowiol 4-88 Ā» ou Ā« Mowiol 8-88 Ā».It is possible, for example, to use the PVA sold under the reference "Mowiol" by the company Clariant, as more particularly the products referenced "Mowiol 4-88" or "Mowiol 8-88".

La solution de coating peut contenir du PVA dans une proportion comprise entre 5% et 80% en masse par rapport au poids total de la solution de coating, de prƩfƩrence entre 20% et 60% en masse par rapport au poids total de la solution de coating, et de prƩfƩrence encore entre 30% et 55% en masse par rapport au poids total de la solution de coating.The coating solution may contain PVA in a proportion of between 5% and 80% by weight relative to the total weight of the coating solution, preferably between 20% and 60% by weight relative to the total weight of the coating solution. coating, and more preferably between 30% and 55% by weight relative to the total weight of the coating solution.

Un agent humectant peut en outre ĆŖtre utilisĆ© dans la solution pour former le revĆŖtement hydrosoluble. Les agents humectant permettent notamment d'Ć©viter Ć  l'eau de migrer dans la tablette.A humectant may further be used in the solution to form the water-soluble coating. Humectants especially prevent water from migrating into the tablet.

Un tel agent humectant est par exemple choisi parmi la glycĆ©rine, les polyĆ©thylĆØnes glycol, et leur combinaison.Such a humectant is for example selected from glycerine, polyethylene glycol, and their combination.

Parmi les polyĆ©thylĆØnes glycol qui peuvent ĆŖtre utilisĆ©s, on choisira de faƧon prĆ©fĆ©rentielle ceux dont la masse molaire en masse est comprise entre 1000 g/mol et 4000 g/mol.Among the polyethylene glycols which can be used, those with a molar mass of between 1000 g / mol and 4000 g / mol are preferably chosen.

La solution de coating peut contenir des agents humectant dans une proportion infƩrieure ou Ʃgale Ơ 25% en masse par rapport au poids total de la solution de coating, de prƩfƩrence dans une proportion comprise entre 1% et 20% en masse par rapport au poids total de la solution de coating, et de prƩfƩrence encore une proportion comprise entre 2% et 10% en masse par rapport au poids total de la solution de coating.The coating solution may contain humectants in a proportion of less than or equal to 25% by weight relative to the total weight of the coating solution, preferably in a proportion of between 1% and 20% by weight relative to the total weight. of the coating solution, and more preferably a proportion of between 2% and 10% by weight relative to the total weight of the coating solution.

L'agent spƩcifique permettant d'amƩliorer l'efficacitƩ de rinƧage est de prƩfƩrence un agent anti-spotting et/ou anti-filming.The specific agent for improving the rinsing efficiency is preferably an anti-spotting and / or anti-filming agent.

Les agents anti-spotting permettent de supprimer ou de limiter l'apparition du spotting, c'est-Ơ-dire de traces, notamment en Ʃvitant la nuclƩation des gouttes d'eau sur la surface du verre ou de la vaisselle.The anti-spotting agents make it possible to eliminate or limit the appearance of spotting, that is to say traces, in particular by avoiding the nucleation of drops of water on the surface of the glass or dishes.

Les agents anti-filming permettent de limiter ou de supprimer l'apparition de filming, c'est-Ơ-dire l'apparition d'un film ou dƩpƓt blanc.The anti-filming agents make it possible to limit or eliminate the appearance of filming, that is to say the appearance of a film or white deposit.

La solution de coating contient de prƩfƩrence des agents spƩcifiques dans une proportion comprise entre 0,05% et 50% en masse par rapport au poids total de la solution de coating, et de prƩfƩrence encore entre 2% et 20% en masse par rapport au poids total de la solution de coating.The coating solution preferably contains specific agents in a proportion of between 0.05% and 50% by weight relative to the total weight of the coating solution, and more preferably between 2% and 20% by weight relative to the total weight of the coating solution.

De prĆ©fĆ©rence, les agents spĆ©cifiques permettant d'amĆ©liorer l'efficacitĆ© de rinƧage sont des polymĆØres spĆ©cifiques, de prĆ©fĆ©rence des polymĆØres ayant une action anti-spotting et/ou anti-filming.Preferably, the specific agents for improving the rinsing efficiency are specific polymers, preferably polymers having an anti-spotting and / or anti-filming action.

Comme agent anti-spotting, on peut par exemple choisir un composĆ© parmi les polymĆØres carboxylate, les polymĆØres carboxylate modifiĆ©s hydrophobes, en particulier les polymĆØres HASE, et leurs combinaisons. On peut par exemple utiliser l'un des produits commercialisĆ©s par la sociĆ©tĆ© Dow Chemical sous les rĆ©fĆ©rences Ā« acusol 820 Ā», Ā« acusol 460 Ā», ou Ā« acusol 460ND Ā».As an anti-spotting agent, it is possible for example to choose a compound from carboxylate polymers, hydrophobic modified carboxylate polymers, in particular HASE polymers, and combinations thereof. For example, one of the products marketed by the Dow Chemical Company can be used under the references "acusol 820", "acusol 460" or "acusol 460ND".

Comme agent anti-spotting, on peut Ć©galement choisir un composĆ© parmi les copolymĆØres acrylique/styrĆØne modifiĆ©s hydrophobes. On peut par exemple utiliser l'un des produits commercialisĆ©s par la sociĆ©tĆ© AkzoNobel sous les rĆ©fĆ©rences Ā« alcosperse 725 Ā», Ā« alcosperse 747 Ā», ou Ā« alcosperse 747D Ā».As an anti-spotting agent, it is also possible to choose a compound among the hydrophobic modified acrylic / styrene copolymers. One can for example use one of the products marketed by AkzoNobel under the references "alcosperse 725", "alcosperse 747", or "alcosperse 747D".

Comme agent anti-filming, on peut par exemple choisir un composĆ© parmi les copolymĆØres d'acide acrylique et de monomĆØre sulfonĆ©. On peut par exemple utiliser l'un des produits commercialisĆ©s par la sociĆ©tĆ© AkzoNobel sous les rĆ©fĆ©rences Ā« alcopserse 240 Ā», Ā« alcosperse 240D Ā», Ā« alcoguard 4100D Ā», Ā« alcoguard 4160 Ā», ou Ā« alcoguard 4160 Ā».As an anti-filming agent, one can for example choose a compound among the copolymers of acrylic acid and of sulfonated monomer. One can for example use one of the products marketed by AkzoNobel under the references "alcopserse 240", "alcosperse 240D", "alcoguard 4100D", "alcoguard 4160", or "alcoguard 4160".

Comme agent anti-filming, on peut Ć©galement choisir un composĆ© parmi les copolymĆØres d'acide acrylique et d'acide sulfonique. On peut par exemple utiliser le produit commercialisĆ© par la sociĆ©tĆ© Dow Chemical sous la rĆ©fĆ©rence Ā« acusol 588G Ā».As an anti-filming agent, it is also possible to choose a compound among the copolymers of acrylic acid and of sulfonic acid. For example, the product marketed by Dow Chemical under the reference "acusol 588G" may be used.

Comme agent anti-filming, on peut Ć©galement choisir un composĆ© parmi les copolymĆØres d'acide acrylique et d'acide malĆ©ique. On peut par exemple utiliser le produit rĆ©fĆ©rencĆ© Ā« acusol 497NG Ā» commercialisĆ© par la sociĆ©tĆ© Dow Chemical, le produit rĆ©fĆ©rencĆ© Ā« alcosperse175ND Ā» commercialisĆ© par la sociĆ©tĆ© AkzoNobel, ou le produit rĆ©fĆ©rencĆ© Ā« Sokalan CP42 Ā» commercialisĆ© par la sociĆ©tĆ© BASF.As an anti-filming agent, it is also possible to choose a compound among the copolymers of acrylic acid and maleic acid. For example, the product referred to as "acusol 497NG" marketed by Dow Chemical may be used, the product referenced "alcosperse175ND" marketed by AkzoNobel, or the product referenced "Sokalan CP42" marketed by BASF.

La solution de coating peut Ʃgalement contenir un amƩrisant tel que le benzoate de dƩnatonium et/ou du parfum.The coating solution may also contain a bittering agent such as denatonium benzoate and / or perfume.

Le reste de la solution est de l'eau.The rest of the solution is water.

Les diffĆ©rents composĆ©s sont mĆ©langĆ©s Ć  tempĆ©rature ambiante afin de former la solution destinĆ©e Ć  former le revĆŖtement de la tablette dĆ©tergente.The various compounds are mixed at room temperature to form the solution for forming the coating of the detergent tablet.

Le mĆ©lange obtenu est par exemple pulvĆ©risĆ© sur la surface du corps formant la tablette dĆ©tergente, de prĆ©fĆ©rence Ć  tempĆ©rature ambiante Ć  l'aide d'un systĆØme de buse.The resulting mixture is for example sprayed on the surface of the body forming the detergent tablet, preferably at room temperature using a nozzle system.

L'Ć©paisseur du revĆŖtement dĆ©posĆ© Ć  la surface de la tablette dĆ©tergente est comprise par exemple entre 0,05 Āµm et 1000 Āµm, de prĆ©fĆ©rence entre 5 Āµm et 300 Āµm, et de prĆ©fĆ©rence encore entre 15 Āµm et 150 Āµm.The thickness of the coating deposited on the surface of the detergent tablet is for example between 0.05 Ī¼m and 1000 Ī¼m, preferably between 5 Ī¼m and 300 Ī¼m, and more preferably between 15 Ī¼m and 150 Ī¼m.

Le revĆŖtement hydrosoluble dĆ©posĆ© sur la tablette reprĆ©sente de prĆ©fĆ©rence entre 0,5% et 15% de masse totale de la tablette dĆ©tergente, et de prĆ©fĆ©rence encore entre 2% et 5% de la masse de la tablette.The water-soluble coating deposited on the tablet preferably represents between 0.5% and 15% of the total mass of the detergent tablet, and more preferably between 2% and 5% of the mass of the tablet.

Essais comparatifsComparative tests Essai 1 : PulvƩrisation de la solution de coating sur une tablette Test 1: Spraying the coating solution on a tablet

L'objectif de cet essai est de comparer le temps de dĆ©litement et la friabilitĆ© d'une tablette coatĆ©e, c'est-Ć -dire enrobĆ©e d'un revĆŖtement hydrosoluble, et d'une tablette non coatĆ©e, c'est-Ć -dire sans enrobage.The objective of this test is to compare the disintegration time and friability of a coated tablet, that is to say coated with a water-soluble coating, and a non-coated tablet, that is to say say without coating.

Les composƩs utilisƩs dans la formule de chaque tablette sont rƩpartis en trois couches. Ces composƩs sont indiquƩs dans le tableau 1 ci-dessous.The compounds used in the formula of each tablet are divided into three layers. These compounds are shown in Table 1 below.

Les diffƩrentes couches de la tablette sont comprimƩes sur une presse hydraulique de faƧon Ơ former une tablette ayant une masse globale de 16 g. Les forces de prƩ-compression et de compression utilisƩes sont indiquƩes dans le tableau 3 ci-dessous.The different layers of the tablet are compressed on a hydraulic press so as to form a tablet having an overall mass of 16 g. The pre-compression and compression forces used are shown in Table 3 below.

Les formules rĆ©alisĆ©es sont reprises dans le Tableau 1 ci-dessous. Tableau 1 MatiĆØre premiĆØre Tablette nĀ°1 Tablette non-coatĆ©e (% en masse) Tablette nĀ°2 Tablette coatĆ©e (% en masse) Carbonate de sodium 18,98 18,96 Chlorure de sodium 18,46 22,87 Citrate de sodium 17,32 17,32 Colorant bleu 0,01 0,00 Colorant jaune 0,01 0,00 Glucopon 50G (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 1,34 1,34 Hedphosphonate de sodium 0,49 0,49 HomopolymĆØre acrylique 0,86 0,85 Protease 1,21 1,21 Arbocel TF0210 (commercialisĆ© par la sociĆ©tĆ© JRS Rettenmeier) 0,61 0,00 Percarbonate de sodium 13,03 13,03 PEG 1500 (polyĆ©thylĆØne glycol) 4,76 1,00 Silicate de sodium 4,92 4,92 Sulfate de sodium 13,52 13,52 TAED 3,19 3,19 GlycĆ©rine 0,78 0,78 Amylase 0,20 0,20 Dehypon GRA (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 0,33 0,33 TOTAL 100,00 100,00 The formulas made are shown in Table 1 below. <i> Table 1 </ i> Raw material Tablet n Ā° 1 Non-coated tablet (% by mass) Tablet n Ā° 2 Coated tablet (% by mass) Sodium carbonate 18.98 18.96 Sodium chloride 18.46 22.87 Sodium citrate 17.32 17.32 Blue dye 0.01 0.00 Yellow dye 0.01 0.00 Glucopon 50G (nonionic surfactant sold by the company BASF) 1.34 1.34 Sodium hedphosphonate 0.49 0.49 Acrylic homopolymer 0.86 0.85 protease 1.21 1.21 Arbocel TF0210 (marketed by JRS Rettenmeier) 0.61 0.00 Sodium percarbonate 13,03 13,03 PEG 1500 (polyethylene glycol) 4.76 1.00 Sodium silicate 4.92 4.92 Sodium sulphate 13.52 13.52 DAT 3.19 3.19 Glycerin 0.78 0.78 amylase 0.20 0.20 Dehypon GRA (nonionic surfactant sold by the company BASF) 0.33 0.33 TOTAL 100.00 100.00

Comme il ressort du Tableau 1, la tablette coatĆ©e (tablette nĀ°2) est identique Ć  la tablette non-coatĆ©e (tablette nĀ°1), sauf pour les ingrĆ©dients suivants:

  • PEG 1500 qui est un additif de pastillage (liant) : 1% versus 4.76%
  • Arbocel TF0210 qui est un agent dĆ©sintĆ©grant: 0% versus 0.61%
As shown in Table 1, the coated tablet (tablet # 2) is identical to the uncoated tablet (tablet # 1), except for the following ingredients:
  • PEG 1500 which is a pelletizing additive (binder): 1% versus 4.76%
  • Arbocel TF0210 which is a disintegrating agent: 0% versus 0.61%

Pour la tablette coatĆ©e, la composition de la solution pour former le revĆŖtement hydrosoluble est rĆ©capitulĆ©e dans le Tableau 2 ci-dessous. Un revĆŖtement uniforme d'une masse totale de 0,4 g est dĆ©posĆ© sur la surface de la tablette de sorte Ć  former un enrobage. Tableau 2 MatiĆØre premiĆØre Solution de coating (% en masse) Alcool polyvinylique 45.84 Eau 47.91 GlycĆ©rine 0 Acusol 460 ND 6.25 For the coated tablet, the composition of the solution to form the water-soluble coating is summarized in Table 2 below. A uniform coating with a total mass of 0.4 g is deposited on the surface of the tablet so as to form a coating. <i> Table 2 </ i> Raw material Coating solution (% by weight) Polyvinyl alcohol 45.84 Water 47.91 Glycerin 0 Acusol 460 ND 6.25

Une fois les deux types de tablettes formƩes, il a ƩtƩ rƩalisƩ plusieurs essais comparatifs, pour mesurer notamment la duretƩ, le dƩlitement, et la friabilitƩ des tablettes.Once the two types of tablets were formed, several comparative tests were carried out, in particular to measure the hardness, the disintegration, and the friability of the tablets.

La duretĆ© des tablettes a Ć©tĆ© mesurĆ©e sur un duromĆØtre de type MTS.The hardness of the tablets was measured on an MTS durometer.

Le temps de dĆ©litement des tablettes obtenues a Ć©tĆ© mesurĆ© sur un Ć©quipement qui fait des vas et viens avec une frĆ©quence de 60 coups/min. Les tablettes sont placĆ©es dans un panier muni de multiples trous pour laisser passer l'eau. Les paniers sont ensuite trempĆ©s dans des bĆ©chers de 1.8L d'eau Ć  30Ā°C. Le temps de dĆ©litement est notĆ© une fois que la tablette est complĆØtement dĆ©sintĆ©grĆ©e et qu'il n'y a plus de rĆ©sidus de tablette dans le panier.The disintegration time of the tablets obtained was measured on equipment that goes back and forth with a frequency of 60 strokes / min. The shelves are placed in a basket with multiple holes to let the water through. The baskets are then soaked in 1.8L beakers of water at 30 Ā° C. The disintegration time is noted a once the tablet is completely disintegrated and there are no more tablet residues in the basket.

La friabilitĆ© des tablettes est mesurĆ©e sur le dispositif de test de friabilitĆ© portant la rĆ©fĆ©rence Ā« FT2 Ā» et commercialisĆ© par la sociĆ©tĆ© SOTAX, avec les paramĆØtres de rotation suivants:

  • nombre de tour: 50
  • vitesse : 25 tours/min
The friability of the tablets is measured on the friability test device bearing the reference "FT2" and marketed by the company SOTAX, with the following rotation parameters:
  • number of turns: 50
  • speed: 25 rpm

Les rĆ©sultats des essais comparatifs sont rĆ©capitulĆ©s dans le Tableau 3 ci-dessous. Tableau 3 Force de prĆ©-compression (kN) Force de compression (kN) DuretĆ© tablette (N) Temps de dĆ©litement (min) % friabilitĆ© Tablette nĀ°1 (non-coatĆ©e) 20 60 90 7 12 Tablette nĀ°2 (coatĆ©e) 10 40 32 3 0.2 The results of the comparative tests are summarized in Table 3 below. <i> Table 3 </ i> Pre-compression force (kN) Compression force (kN) Tablet hardness (N) Disintegration time (min) % friability Tablet n Ā° 1 (uncoated) 20 60 90 7 12 Tablet # 2 (Coated) 10 40 32 3 0.2

On constate avec les rĆ©sultats des essais comparatifs rĆ©capitulĆ© dans le tableau 3 que l'utilisation du revĆŖtement hydrosoluble permet :

  • de rĆ©duire la quantitĆ© d'additif de pastillage (liant, agent dĆ©sintĆ©grant) dans la formule ;
  • de rĆ©duire les forces de prĆ©-compression et compression sur les presses ;
  • de diminuer le temps de dĆ©litement des tablettes ;
  • tout en obtenant des tablettes moins friables, c'est-Ć -dire plus stables dans le temps, notamment en conditions de stockage.
It can be seen from the results of the comparative tests recapitulated in Table 3 that the use of the water-soluble coating makes it possible:
  • to reduce the amount of pelletizing additive (binder, disintegrant) in the formula;
  • reduce pre-compression and compression forces on presses;
  • to reduce the disintegration time of tablets;
  • while obtaining less friable tablets, that is to say, more stable over time, especially in storage conditions.

Essai 2 : Utilisation d'un agent anti-spotting dans la solution de coating pour amƩliorer l'efficacitƩ de rinƧage d'une tablette lave-vaisselle Test 2 : Use of an anti-spotting agent in the coating solution to improve the rinsing efficiency of a dishwasher tablet

L'objectif de cet essai est d'Ʃvaluer l'influence de l'utilisation d'un coating intƩgrant un agent anti-spotting sur l'efficacitƩ de rinƧage des tablettes.The objective of this test is to evaluate the influence of the use of a coating incorporating an anti-spotting agent on the rinsing efficiency of the tablets.

Des mesures comparatives ont ƩtƩ faites sur les tablettes lave-vaisselle suivantes:

  • une tablette lave-vaisselle non-coatĆ©e avec l'agent anti-spotting dans la couche centrale (tablette nĀ°3) ;
  • une tablette lave-vaisselle coatĆ©e avec l'agent anti-spotting dans la couche centrale, oĆ¹ la solution de coating ne contient pas l'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique et d'eau (tablette nĀ°4) ;
  • une tablette lave-vaisselle coatĆ©e avec l'agent anti-spotting dans la couche centrale, oĆ¹ la solution de coating ne contient pas l'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, et d'un agent humectant (tablette nĀ°5) ;
  • une tablette lave-vaisselle enrobĆ©e d'une solution de coating contenant l'agent anti-spotting, oĆ¹ la formulation de la tablette ne contient pas l'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, et de l'agent anti-spotting (tablette nĀ°6)
  • une tablette lave-vaisselle enrobĆ©e d'une solution de coating contenant l'agent anti-spotting, oĆ¹ la formulation de la tablette ne contient pas l'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, d'un agent humectant et de l'agent anti-spotting (tablette nĀ°7).
Comparative measurements have been made on the following dishwasher tablets:
  • a dishwasher dish not coated with the anti-spotting agent in the central layer (tablet n Ā° 3);
  • a dishwasher tablet coated with the anti-spotting agent in the central layer, where the coating solution does not contain the anti-spotting agent. The coating solution is composed of polyvinyl alcohol and water (tablet # 4);
  • a dishwasher tablet coated with the anti-spotting agent in the central layer, where the coating solution does not contain the anti-spotting agent. The solution coating is composed of polyvinyl alcohol, water, and a humectant (tablet # 5);
  • a dishwasher tablet coated with a coating solution containing the anti-spotting agent, wherein the formulation of the tablet does not contain the anti-spotting agent. The coating solution is composed of polyvinyl alcohol, water, and anti-spotting agent (tablet n Ā° 6)
  • a dishwasher tablet coated with a coating solution containing the anti-spotting agent, wherein the formulation of the tablet does not contain the anti-spotting agent. The coating solution is composed of polyvinyl alcohol, water, a humectant and anti-spotting agent (tablet # 7).

L'agent anti-spotting utilisĆ© pour cet essai comparatif est le produit rĆ©fĆ©rencĆ© Ā« acusol 460ND Ā» commercialisĆ© par la sociĆ©tĆ© Dow Chemical.The anti-spotting agent used for this comparative test is the product referred to as "acusol 460ND" marketed by Dow Chemical.

Les composƩs utilisƩs dans la formule de chaque tablette sont rƩpartis en trois couches. Les composƩs des diffƩrentes couches sont indiquƩs dans les tableaux 4a, 4b et 4c ci-dessous.The compounds used in the formula of each tablet are divided into three layers. The compounds of the different layers are shown in Tables 4a, 4b and 4c below.

Les diffĆ©rentes couches de la tablette sont comprimĆ©es sur une presse hydraulique de faƧon Ć  former une tablette ayant une masse globale de 16 g. Les forces de prĆ©-compression et de compression utilisĆ©es sont indiquĆ©es dans le tableau 6 ci-dessous. Tableau 4a IngrĆ©dients COUCHE 1 Tablette nĀ°3 (% en masse de la couche) Tablette nĀ°4 (% en masse de la couche) Tablette nĀ°5 (% en masse de la couche) Tablette nĀ°6 (% en masse de la couche) Tablette nĀ°7 (% en masse de la couche) CARBONATE DE SODIUM 11,80 11,80 11,80 11,80 11,80 CITRATE TRISODIQUE 2(H2O) 40,45 40,45 40,45 40,45 40,45 PERCARBONATE DE SODIUM 23,27 23,27 23,27 23,27 23,27 CHLORURE DE SODIUM 14,56 14,56 14,56 14,56 14,56 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 PEG 1500 5,00 5,00 5,00 5,00 5,00 HEDPHOSPHONATE DE SODIUM 0,88 0,88 0,88 0,88 0,88 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 1 100,00 100,00 100,00 100,00 100,00 Tableau 4b IngrĆ©dients COUCHE 2 Tablette nĀ°3 (% en masse de la couche) Tablette nĀ°4 (% en masse de la couche) Tablette nĀ°5 (% en masse de la couche) Tablette nĀ°6 (% en masse de la couche) Tablette nĀ°7 (% en masse de la couche) CARBONATE DE SODIUM 11,77 11,77 11,77 11,77 11,77 CITRATE TRISODIQUE 2(H2O) 40,45 40,45 40,45 40,45 40,45 PERCARBONATE DE SODIUM 23,27 23,27 23,27 23,27 23,27 CHLORURE DE SODIUM 13.98 13.98 13.98 14.56 14.56 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 PEG 1500 5,00 5,00 5,00 5,00 5,00 HEDPHOSPHONATE DE SODIUM 0,88 0,88 0,88 0,88 0,88 ACUSOL 460ND 0.58 0.58 0.58 0 0 COLORANT TARTRAZINE E102 MD LA 0,03 0,03 0,03 0,03 0,03 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 2 100,00 100,00 100,00 100,00 100,00 Tableau 4c IngrĆ©dients COUCHE 3 Tablette nĀ°3 (% en masse de la couche) Tablette nĀ°4 (% en masse de la couche) Tablette nĀ°5 (% en masse de la couche) Tablette nĀ°6 (% en masse de la couche) Tablette nĀ°7 (% en masse de la couche) CARBONATE DE SODIUM 13,10 13,10 13,10 13,10 13,10 SILICATE DE SODIUM 8,80 8,80 8,80 8,80 8,80 CITRATE TRISODIQUE 2(H2O) 27,80 27,80 27,80 27,80 27,80 Parfum citron 0,06 0,06 0,06 0,06 0,06 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 CHLORURE DE SODIUM 29,85 29,85 29,85 29,85 29,85 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 TAED 4,00 4,00 4,00 4,00 4,00 CATALYSEUR 0,76 0,76 0,76 0,76 0,76 PROTEASE 4,65 4,65 4,65 4,65 4,65 AMYLASE 0,78 0,78 0,78 0,78 0,78 PEG 1500 6,13 6,13 6,13 6,13 6,13 COLORANT BLEU E133 LAKE 0,03 0,03 0,03 0,03 0,03 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 3 100,00 100,00 100,00 100,00 100,00 The different layers of the tablet are compressed on a hydraulic press so as to form a tablet having an overall mass of 16 g. The pre-compression and compression forces used are shown in Table 6 below. <i> Table 4a </ i> Ingredients LAYER 1 Tablet n Ā° 3 (% by mass of the layer) Tablet 4 (% by weight of the layer) Tablet n Ā° 5 (% by weight of the layer) Tablet n Ā° 6 (% by mass of the layer) Tablet 7 (% by weight of the layer) SODIUM CARBONATE 11.80 11.80 11.80 11.80 11.80 TRISODIC CITRATE 2 (H2O) 40,45 40,45 40,45 40,45 40,45 SODIUM PERCARBONATE 23.27 23.27 23.27 23.27 23.27 SODIUM CHLORIDE 14.56 14.56 14.56 14.56 14.56 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 PEG 1500 5.00 5.00 5.00 5.00 5.00 SODIUM HEDPHOSPHONATE 0.88 0.88 0.88 0.88 0.88 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 1 100.00 100.00 100.00 100.00 100.00 Ingredients LAYER 2 Tablet n Ā° 3 (% by mass of the layer) Tablet 4 (% by weight of the layer) Tablet n Ā° 5 (% by weight of the layer) Tablet n Ā° 6 (% by mass of the layer) Tablet 7 (% by weight of the layer) SODIUM CARBONATE 11.77 11.77 11.77 11.77 11.77 TRISODIC CITRATE 2 (H2O) 40,45 40,45 40,45 40,45 40,45 SODIUM PERCARBONATE 23.27 23.27 23.27 23.27 23.27 SODIUM CHLORIDE 13.98 13.98 13.98 14.56 14.56 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 PEG 1500 5.00 5.00 5.00 5.00 5.00 SODIUM HEDPHOSPHONATE 0.88 0.88 0.88 0.88 0.88 ACUSOL 460ND 0.58 0.58 0.58 0 0 TARTRAZINE COLOR E102 Ā® LA 0.03 0.03 0.03 0.03 0.03 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 2 100.00 100.00 100.00 100.00 100.00 Ingredients LAYER 3 Tablet n Ā° 3 (% by mass of the layer) Tablet 4 (% by weight of the layer) Tablet n Ā° 5 (% by weight of the layer) Tablet n Ā° 6 (% by mass of the layer) Tablet 7 (% by weight of the layer) SODIUM CARBONATE 13,10 13,10 13,10 13,10 13,10 SODIUM SILICATE 8.80 8.80 8.80 8.80 8.80 TRISODIC CITRATE 2 (H2O) 27,80 27,80 27,80 27,80 27,80 Lemon perfume 0.06 0.06 0.06 0.06 0.06 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 SODIUM CHLORIDE 29.85 29.85 29.85 29.85 29.85 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 DAT 4.00 4.00 4.00 4.00 4.00 CATALYST 0.76 0.76 0.76 0.76 0.76 Protease 4.65 4.65 4.65 4.65 4.65 AMYLASE 0.78 0.78 0.78 0.78 0.78 PEG 1500 6.13 6.13 6.13 6.13 6.13 BLUE COLOR E133 LAKE 0.03 0.03 0.03 0.03 0.03 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 3 100.00 100.00 100.00 100.00 100.00

Pour les tablettes nĀ°4, nĀ°5, nĀ°6 et nĀ°7, une solution de coating est pulvĆ©risĆ©e Ć  la surface des tablettes ainsi formĆ©es afin d'enrober la tablette avec un revĆŖtement hydrosoluble.For tablets No. 4, No. 5, No. 6 and No. 7, a coating solution is sprayed on the surface of tablets thus formed to coat the tablet with a water-soluble coating.

Le tableau 5 ci-dessous prĆ©cise la composition de la solution de coating utilisĆ©e pour ces tablettes nĀ°4, nĀ°5, nĀ°6 et nĀ°7. Tableau 5 IngrĆ©dients solution coating Tablette nĀ°4 (% en masse) Tablette nĀ°5 (% en masse) Tablette nĀ°6 (% en masse) Tablette nĀ°7 (% en masse) Alcool polyvinylique 47,90 47,90 45,84 45,84 Eau 52,10 50,10 47,91 46,91 GlycĆ©rine 0 2,00 0 1,00 Acusol 460 ND 0 0 6,25 6,25 TOTAL 100,00 100,00 100,00 100,00 Table 5 below specifies the composition of the coating solution used for these tablets No. 4, No. 5, No. 6 and No. 7. <i> Table 5 </ i> Ingredients solution coating Tablet # 4 (% by weight) Tablet # 5 (% by weight) Tablet # 6 (% by weight) Tablet # 7 (% by weight) Polyvinyl alcohol 47,90 47,90 45.84 45.84 Water 52.10 50,10 47.91 46.91 Glycerin 0 2.00 0 1.00 Acusol 460 ND 0 0 6.25 6.25 TOTAL 100.00 100.00 100.00 100.00

Pour les tablettes nĀ°4 et nĀ°5, un revĆŖtement uniforme de 0,4 g de solution de coating est dĆ©posĆ© sur la surface de la tablette afin de former un enrobage uniforme.For tablets # 4 and # 5, a uniform coating of 0.4 g of coating solution is deposited on the surface of the tablet to form a uniform coating.

Pour les tablettes nĀ°6 et nĀ°7, un revĆŖtement uniforme de 0,465 g de solution de coating est dĆ©posĆ© sur la surface de la tablette afin de former un enrobage uniforme.For tablets # 6 and # 7, a uniform coating of 0.465 g of coating solution is deposited on the surface of the tablet to form a uniform coating.

Chacune des tablettes nĀ°3, nĀ°4, nĀ°5, nĀ°6 et nĀ°7 ainsi fabriquĆ©es comprennent la mĆŖme quantitĆ© d'agent anti-spotting, Ć  savoir 0,029 g de produit Ā« Acusol 460 ND Ā».Each of tablets No. 3, No. 4, No. 5, No. 6 and No. 7 thus manufactured comprise the same amount of anti-spotting agent, namely 0.029 g of "Acusol 460 ND" product.

Le tableau 6 ci-dessous rĆ©capitule les paramĆØtres de fabrication des diffĆ©rentes tablettes, et donne les mesures de duretĆ© et dĆ©litement de chacune des tablettes, Ć©tant entendu que ces paramĆØtres ont Ć©tĆ© mesurĆ©s de la mĆŖme faƧon que pour l'essai 1. Tableau 6 Tablette nĀ°3 Tablette nĀ°4 Tablette nĀ°5 Tablette nĀ°6 Tablette nĀ°7 Masse couche 1 (g) 6 6 6 6 6 Masse couche 2 (g) 5 5 5 5 5 Masse couche 3 (g) 5 5 5 5 5 Force de prĆ©-compression appliquĆ©e sur couche 1 (kN) 20 30 30 30 30 Force de prĆ©-compression appliquĆ©e sur couche 2 (kN) 20 20 20 20 20 Force de compression appliquĆ©e sur couche 3 (kN) 60 30 30 30 30 DuretĆ© tablette (N) 135 52 51 48 49 Temps de dĆ©litement (min:sec) de la tablette sans coating 7min:30sec 4min:40sec 4min:30sec 4min:10sec 4min:05sec Table 6 below summarizes the manufacturing parameters of the different tablets, and gives the measurements of hardness and disintegration of each of the tablets, it being understood that these parameters were measured in the same way as for the test 1. <i> Table 6 </ i> Tablet n Ā° 3 Tablet n Ā° 4 Tablet n Ā° 5 Tablet n Ā° 6 Tablet n Ā° 7 Mass layer 1 (g) 6 6 6 6 6 Mass layer 2 (g) 5 5 5 5 5 Mass layer 3 (g) 5 5 5 5 5 Pre-compression force applied on layer 1 (kN) 20 30 30 30 30 Pre-compression force applied on layer 2 (kN) 20 20 20 20 20 Compression force applied on layer 3 (kN) 60 30 30 30 30 Tablet hardness (N) 135 52 51 48 49 Disintegration time (min: sec) of the tablet without coating 7min: 30sec 4min: 40sec 4min: 30sec 4min: 10sec 4min: 05sec

Il a par ailleurs Ć©tĆ© effectuĆ© des tests afin d'Ć©valuer pour chacune des tablettes nĀ°3, nĀ°4, nĀ°5, nĀ°6 et nĀ°7 l'efficacitĆ© de rinƧage associĆ©e.In addition, tests were carried out to evaluate the associated rinsing efficiency for each of tablets # 3, # 4, # 5, # 6 and # 7.

Les tests pour mesurer l'efficacitĆ© de rinƧage des tablettes ont Ć©tĆ© rĆ©alisĆ©s avec un lave-vaisselle de la marque Fagor LFF-041 programmĆ© selon un cycle de lavage court (30 minutes) Ć  35Ā°C et avec une duretĆ© d'eau 35Ā°TH.The tests to measure the rinsing efficiency of the tablets were carried out with a Fagor LFF-041 dishwasher programmed in a short wash cycle (30 minutes) at 35 Ā° C and a water hardness of 35 Ā° C. TH.

Pour ce test, 4 verres gobelets sont placƩs sur le compartiment supƩrieur du lave-vaisselle au dƩbut du cycle de lavage. Un ballaste de salissure est Ʃgalement placƩ dans le lave-vaisselle.For this test, 4 cup glasses are placed on the top compartment of the dishwasher at the beginning of the wash cycle. A dirt ballast is also placed in the dishwasher.

L'efficacitƩ de rinƧage des tablettes est ƩvaluƩe par observation des verres Ơ l'aide d'un caisson muni de spots.The rinsing efficiency of the tablets is evaluated by observation of the glasses using a box with spots.

Le spotting est mesurĆ© aprĆØs un cycle de lavage. Le spotting est Ć©valuĆ© grĆ¢ce Ć  une Ć©chelle de notes entre 0 et 7, oĆ¹ 0 est la plus mauvaise note (rinƧage inefficace) et 7 est la meilleure note (rinƧage trĆØs efficace).Spotting is measured after a wash cycle. Spotting is rated on a scale of scores between 0 and 7, where 0 is the worst score (ineffective rinse) and 7 is the best rating (very effective rinse).

Le filming est mesurĆ© aprĆØs 5 cycles de lavage successifs. Le filming est Ć©valuĆ© par observation du voile prĆ©sent sur les verres. Le filming est Ć©valuĆ© grĆ¢ce Ć  une Ć©chelle de notes entre 0 et 10, oĆ¹ 0 est la plus mauvaise note (rinƧage inefficace) et 10 est la meilleure note (rinƧage trĆØs efficace).The filming is measured after 5 successive washing cycles. The filming is evaluated by observation of the veil present on the glasses. Filming is rated with a rating scale between 0 and 10, where 0 is the worst rating (ineffective rinsing) and 10 is the best rating (very effective rinsing).

La brillance est Ć©valuĆ©e aprĆØs 1 cycle de lavage. La brillance est Ć©valuĆ©e grĆ¢ce Ć  l'Ć©chelle de notes de 0 Ć  10, oĆ¹ 0 est la plus mauvaise note (rinƧage inefficace) et 10 est la meilleure note (rinƧage trĆØs efficace).The gloss is evaluated after 1 wash cycle. The brilliance is evaluated thanks to the scale of notes of 0 to 10, where 0 is the worst note (ineffective rinsing) and 10 is the best note (rinsing very effective).

Les rĆ©sultats des essais comparatifs sont rĆ©capitulĆ©s dans le Tableau 7 ci-dessous. Tableau 7 Coating Spotting Filming Brillance Tablette nĀ°3 NON 5 9 10 Tablette nĀ°4 OUI sans Acusol 460ND 5.5 9 10 Tablette nĀ°5 OUI sans Acusol 460ND 5.5 9 10 Tablette nĀ°6 OUI avec Acusol 460ND 6.5 9 10 Tablette nĀ°7 OUI avec Acusol 460ND 6.5 9 10 The results of the comparative tests are summarized in Table 7 below. <i> Table 7 </ i> coating spotting Filming brightness Tablet n Ā° 3 NO 5 9 10 Tablet n Ā° 4 YES without Acusol 460ND 5.5 9 10 Tablet n Ā° 5 YES without Acusol 460ND 5.5 9 10 Tablet n Ā° 6 YES with Acusol 460ND 6.5 9 10 Tablet n Ā° 7 YES with Acusol 460ND 6.5 9 10

On constate que les tablettes nĀ°5 et nĀ°6 prĆ©sentent de meilleurs rĆ©sultats sur le spotting que les tablettes nĀ°3, nĀ°4 et nĀ°5.It is found that tablets # 5 and # 6 have better results on spotting than tablets # 3, # 4 and # 5.

L'ajout de l'agent anti-spotting (Acusol 460 ND) dans la solution de coating permet donc d'augmenter l'efficacitƩ de rinƧage sur le spotting en cycle court.The addition of the anti-spotting agent (Acusol 460 ND) in the coating solution therefore makes it possible to increase the rinsing efficiency on the short cycle spotting.

La dispersion rapide de l'agent anti-spotting (Acusol 460 ND) dans la solution de lavage permet en effet d'amƩliorer l'efficacitƩ sur le spotting de la tablette.The rapid dispersion of the anti-spotting agent (Acusol 460 ND) in the washing solution makes it possible to improve the efficiency on the spotting of the tablet.

Essai 3 : Utilisation d'un polymĆØre anti-spotting dans la solution de coating pour amĆ©liorer la stabilitĆ© d'une tablette lave-vaisselle Test 3 : Use of an anti-spotting polymer in the coating solution to improve the stability of a dishwasher tablet

L'objectif de cet essai est d'Ʃvaluer l'influence de l'utilisation d'un coating intƩgrant un agent anti-spotting sur la stabilitƩ des tablettes.The objective of this test is to evaluate the influence of the use of a coating incorporating an anti-spotting agent on the shelf stability.

Des mesures comparatives ont ƩtƩ faites sur les tablettes lave-vaisselle suivantes:

  • une tablette lave-vaisselle non-coatĆ©e Ć©tant emballĆ©e individuellement dans un emballage hydrosoluble, de type flowpack hydrosoluble (tablette nĀ°8) ;
  • une tablette lave-vaisselle coatĆ©e, oĆ¹ la solution de coating ne contient pas d'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique et d'eau (tablette nĀ°9) ;
  • une tablette lave-vaisselle coatĆ©e, oĆ¹ la solution de coating ne contient pas d'agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, et d'un agent humectant (tablette nĀ°10) ;
  • une tablette lave-vaisselle enrobĆ©e d'une solution de coating contenant un agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, et de l'agent anti-spotting (tablette nĀ°11) ;
  • une tablette lave-vaisselle enrobĆ©e d'une solution de coating contenant un agent anti-spotting. La solution de coating est composĆ©e d'alcool polyvinylique, d'eau, d'un agent humectant et de l'agent anti-spotting (tablette nĀ°12).
Comparative measurements have been made on the following dishwasher tablets:
  • a non-coated dishwashing tablet being individually wrapped in a water-soluble, water-soluble flowpack (tablet # 8);
  • a coated dishwasher tablet, where the coating solution does not contain an anti-spotting agent. The coating solution is composed of polyvinyl alcohol and water (tablet n Ā° 9);
  • a coated dishwasher tablet, where the coating solution does not contain an anti-spotting agent. The coating solution is composed of polyvinyl alcohol, water, and a humectant (tablet # 10);
  • a dishwasher tablet coated with a coating solution containing an anti-spotting agent. The coating solution is composed of polyvinyl alcohol, water, and anti-spotting agent (tablet # 11);
  • a dishwasher tablet coated with a coating solution containing an anti-spotting agent. The coating solution is composed of polyvinyl alcohol, water, a humectant and anti-spotting agent (tablet # 12).

L'agent anti-spotting utilisĆ© pour cet essai comparatif est le produit rĆ©fĆ©rencĆ© Ā« acusol 460ND Ā» commercialisĆ© par la sociĆ©tĆ© Dow Chemical.The anti-spotting agent used for this comparative test is the product referred to as "acusol 460ND" marketed by Dow Chemical.

Les composƩs utilisƩs dans la formule de chaque tablette sont rƩpartis en trois couches. Les composƩs des diffƩrentes couches sont indiquƩs dans les tableaux 8a, 8b et 8c ci-dessous.The compounds used in the formula of each tablet are divided into three layers. The compounds of the different layers are shown in Tables 8a, 8b and 8c below.

Les diffĆ©rentes couches de la tablette sont comprimĆ©es sur une presse hydraulique de faƧon Ć  former une tablette ayant une masse globale de 16 g. Les forces de prĆ©-compression et de compression utilisĆ©es sont indiquĆ©es dans le tableau 10 ci-dessous. Tableau 8a IngrĆ©dients COUCHE 1 Tablette nĀ°8 (% en masse de la couche) Tablette nĀ°9 (% en masse de la couche) Tablette nĀ°10 (% en masse de la couche) Tablette nĀ°11 (% en masse de la couche) Tablette nĀ°12 (% en masse de la couche) CARBONATE DE SODIUM 11,80 11,80 11,80 11,80 11,80 CITRATE TRISODIQUE 2(H2O) 40,45 40,45 40,45 40,45 40,45 PERCARBONATE DE SODIUM 23,27 23,27 23,27 23,27 23,27 CHLORURE DE SODIUM 14,56 14,56 14,56 14,56 14,56 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 PEG 1500 5,00 5,00 5,00 5,00 5,00 HEDPHOSPHONATE DE SODIUM 0,88 0,88 0,88 0,88 0,88 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 1 100,00 100,00 100,00 100,00 100,00 Tableau 8b IngrĆ©dients COUCHE 2 Tablette nĀ°8 (% en masse de la couche) Tablette nĀ°9 (% en masse de la couche) Tablette nĀ°10 (% en masse de la couche) Tablette nĀ°11 (% en masse de la couche) Tablette nĀ°12 (% en masse de la couche) CARBONATE DE SODIUM 11,77 11,77 11,77 11,77 11,77 CITRATE TRISODIQUE 2(H2O) 40,45 40,45 40,45 40,45 40,45 PERCARBONATE DE SODIUM 23,27 23,27 23,27 23,27 23,27 CHLORURE DE SODIUM 14,56 14,56 14,56 14,56 14,56 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 PEG 1500 5,00 5,00 5,00 5,00 5,00 HEDPHOSPHONATE DE SODIUM 0,88 0,88 0,88 0,88 0,88 COLORANT TARTRAZINE E102 MD LA 0,03 0,03 0,03 0,03 0,03 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 2 100,00 100,00 100,00 100,00 100,00 Tableau 8c IngrĆ©dients COUCHE 3 Tablette nĀ°8 (% en masse de la couche) Tablette nĀ°9 (% en masse de la couche) Tablette nĀ°10 (% en masse de la couche) Tablette nĀ°11 (% en masse de la couche) Tablette nĀ°12 (% en masse de la couche) CARBONATE DE SODIUM 13,10 13,10 13,10 13,10 13,10 SILICATE DE SODIUM 8,80 8,80 8,80 8,80 8,80 CITRATE TRISODIQUE 2(H2O) 27,80 27,80 27,80 27,80 27,80 Parfum citron 0,06 0,06 0,06 0,06 0,06 LUTENSOL AT50 (Tensioactif non ionique commercialisĆ© par la sociĆ©tĆ© BASF) 2,98 2,98 2,98 2,98 2,98 CHLORURE DE SODIUM 29,85 29,85 29,85 29,85 29,85 ARBOCEL TF 0210 0,86 0,86 0,86 0,86 0,86 TAED 4,00 4,00 4,00 4,00 4,00 CATALYSEUR 0,76 0,76 0,76 0,76 0,76 PROTEASE 4,65 4,65 4,65 4,65 4,65 AMYLASE 0,78 0,78 0,78 0,78 0,78 PEG 1500 6,13 6,13 6,13 6,13 6,13 COLORANT BLEU E133 LAKE 0,03 0,03 0,03 0,03 0,03 GLYCERINE 0,20 0,20 0,20 0,20 0,20 TOTAL COUCHE 3 100,00 100,00 100,00 100,00 100,00 The different layers of the tablet are compressed on a hydraulic press so as to form a tablet having an overall mass of 16 g. The pre-compression and compression forces used are shown in Table 10 below. <i> Table 8a </ i> Ingredients LAYER 1 Tablet n Ā° 8 (% by mass of the layer) Tablet 9 (% by weight of the layer) Tablet n Ā° 10 (% in mass of the layer) Tablet n Ā° 11 (% by mass of the layer) Tablet 12 (% by weight of the layer) SODIUM CARBONATE 11.80 11.80 11.80 11.80 11.80 TRISODIC CITRATE 2 (H2O) 40,45 40,45 40,45 40,45 40,45 SODIUM PERCARBONATE 23.27 23.27 23.27 23.27 23.27 SODIUM CHLORIDE 14.56 14.56 14.56 14.56 14.56 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 PEG 1500 5.00 5.00 5.00 5.00 5.00 SODIUM HEDPHOSPHONATE 0.88 0.88 0.88 0.88 0.88 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 1 100.00 100.00 100.00 100.00 100.00 Ingredients LAYER 2 Tablet n Ā° 8 (% by mass of the layer) Tablet 9 (% by weight of the layer) Tablet n Ā° 10 (% in mass of the layer) Tablet n Ā° 11 (% by mass of the layer) Tablet 12 (% by weight of the layer) SODIUM CARBONATE 11.77 11.77 11.77 11.77 11.77 TRISODIC CITRATE 2 (H2O) 40,45 40,45 40,45 40,45 40,45 SODIUM PERCARBONATE 23.27 23.27 23.27 23.27 23.27 SODIUM CHLORIDE 14.56 14.56 14.56 14.56 14.56 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 PEG 1500 5.00 5.00 5.00 5.00 5.00 SODIUM HEDPHOSPHONATE 0.88 0.88 0.88 0.88 0.88 TARTRAZINE COLOR E102 Ā® LA 0.03 0.03 0.03 0.03 0.03 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 2 100.00 100.00 100.00 100.00 100.00 Ingredients LAYER 3 Tablet n Ā° 8 (% by mass of the layer) Tablet 9 (% by weight of the layer) Tablet n Ā° 10 (% in mass of the layer) Tablet n Ā° 11 (% by mass of the layer) Tablet 12 (% by weight of the layer) SODIUM CARBONATE 13,10 13,10 13,10 13,10 13,10 SODIUM SILICATE 8.80 8.80 8.80 8.80 8.80 TRISODIC CITRATE 2 (H2O) 27,80 27,80 27,80 27,80 27,80 Lemon perfume 0.06 0.06 0.06 0.06 0.06 LUTENSOL AT50 (nonionic surfactant sold by the company BASF) 2.98 2.98 2.98 2.98 2.98 SODIUM CHLORIDE 29.85 29.85 29.85 29.85 29.85 ARBOCEL TF 0210 0.86 0.86 0.86 0.86 0.86 DAT 4.00 4.00 4.00 4.00 4.00 CATALYST 0.76 0.76 0.76 0.76 0.76 Protease 4.65 4.65 4.65 4.65 4.65 AMYLASE 0.78 0.78 0.78 0.78 0.78 PEG 1500 6.13 6.13 6.13 6.13 6.13 BLUE COLOR E133 LAKE 0.03 0.03 0.03 0.03 0.03 GLYCERIN 0.20 0.20 0.20 0.20 0.20 TOTAL LAYER 3 100.00 100.00 100.00 100.00 100.00

Chacune des tablettes nĀ°8 fabriquĆ©es sont emballĆ©es individuellement dans un flowpack hydrosoluble. Un tel flowpack hydrosoluble est un emballage formĆ© Ć  partir d'alcool polyvinylique, d'Ć©paisseur 35 Āµm, comme par exemple le produit rĆ©fĆ©rencĆ© Ā« L711 Ā» commercialisĆ© par la sociĆ©tĆ© MonoSol.Each of the manufactured tablets # 8 are individually wrapped in a water-soluble flowpack. Such a water-soluble flowpack is a package formed from polyvinyl alcohol, of thickness 35 Ī¼m, such as for example the product referenced "L711" marketed by the company MonoSol.

Pour les tablettes nĀ°9, nĀ°10, nĀ°11 et nĀ°12, une solution de coating est pulvĆ©risĆ©e Ć  la surface des tablettes ainsi formĆ©es afin d'enrober la tablette avec un revĆŖtement hydrosoluble. Pour ces tablettes, un revĆŖtement uniforme de 0,5 g de solution de coating est dĆ©posĆ© sur la surface de la tablette afin de former un enrobage uniforme.For tablets No. 9, No. 10, No. 11 and No. 12, a coating solution is sprayed on the surface of tablets thus formed to coat the tablet with a water-soluble coating. For these tablets, a uniform coating of 0.5 g coating solution is deposited on the surface of the tablet to form a uniform coating.

Le tableau 9 ci-dessous prĆ©cise la composition de la solution de coating utilisĆ©e pour ces tablettes nĀ°9, nĀ°10, nĀ°11 et nĀ°12. Tableau 9 IngrĆ©dients solution coating Tablette nĀ°9 (% en masse) Tablette nĀ°10 (% en masse) Tablette nĀ°11 (% en masse) Tablette nĀ°12 (% en masse) Alcool polyvinylique 47,90 47,90 45,84 45,84 Eau 52,10 50,10 47,91 46,91 GlycĆ©rine 0 2,00 0 1,00 Acusol 460 ND 0 0 6,25 6,25 TOTAL 100,00 100,00 100,00 100,00 Table 9 below specifies the composition of the coating solution used for these tablets No. 9, No. 10, No. 11 and No. 12. <i> Table 9 </ i> Ingredients solution coating Tablet n Ā° 9 (% in mass) Tablet # 10 (% by weight) Tablet n Ā° 11 (% in mass) Tablet # 12 (% by weight) Polyvinyl alcohol 47,90 47,90 45.84 45.84 Water 52.10 50,10 47.91 46.91 Glycerin 0 2.00 0 1.00 Acusol 460 ND 0 0 6.25 6.25 TOTAL 100.00 100.00 100.00 100.00

Le tableau 10 ci-dessous rĆ©capitule les paramĆØtres de fabrication des diffĆ©rentes tablettes, et donne les mesures de duretĆ© et dĆ©litement de chacune des tablettes, Ć©tant entendu que ces paramĆØtres ont Ć©tĆ© mesurĆ©s de la mĆŖme faƧon que pour l'essai 1. Tableau 10 Tablette nĀ°8 Tablette nĀ°9 Tablette nĀ°10 Tablette nĀ°11 Tablette nĀ°12 Masse couche 1 (g) 6 6 6 6 6 Masse couche 2 (g) 5 5 5 5 5 Masse couche 3 (g) 5 5 5 5 5 Force de prĆ©-compression appliquĆ©e sur couche 1 (kN) 20 30 30 30 30 Force de prĆ©-compression appliquĆ©e sur couche 2 (kN) 20 20 20 20 20 Force de prĆ©-compression appliquĆ©e sur couche 3 (kN) 60 30 30 30 30 DuretĆ© tablette (N) 135 50 49 51 50 Temps de dĆ©litement (min:sec) de la tablette sans coating et sans flowpack 7min 20sec 4min 52sec 4min 50sec 5min 00sec 5min 05sec Table 10 below summarizes the manufacturing parameters of the various tablets, and gives the measurements of hardness and disintegration of each of the tablets, it being understood that these parameters were measured in the same way as for the test 1. <i> Table 10 </ i> Tablet n Ā° 8 Tablet n Ā° 9 Tablet n Ā° 10 Tablet n Ā° 11 Tablet n Ā° 12 Mass layer 1 (g) 6 6 6 6 6 Mass layer 2 (g) 5 5 5 5 5 Mass layer 3 (g) 5 5 5 5 5 Pre-compression force applied on layer 1 (kN) 20 30 30 30 30 Pre-compression force applied on layer 2 (kN) 20 20 20 20 20 Pre-compression force applied on layer 3 (kN) 60 30 30 30 30 Tablet hardness (N) 135 50 49 51 50 Disintegration time (min: sec) of the tablet without coating and without flowpack 7min 20sec 4min 52sec 4min 50sec 5min 00sec 5min 05sec

Pour l'essai 3, on utilise 5 exemplaires de chacune des tablettes nĀ°8, nĀ°9, nĀ°10, nĀ°11 et nĀ°12 et l'on place ces 5 exemplaires dans un sachet souple dont la forme est prĆ©vue pour que le sachet tienne debout seul, par exemple un sachet de type Doypack.For test 3, 5 copies of each of tablets No. 8, No. 9, No. 10, No. 11 and No. 12 are used and these 5 are placed in a flexible bag whose shape is provided. for the bag to stand alone, for example a Doypack type bag.

Chaque sachet souple contenant les 5 exemplaires de chacune des diffĆ©rentes tablettes est ensuite placĆ© dans une enceinte climatique Ć  38Ā°C et 70% d'humiditĆ© relative pendant 2 semaines.Each flexible bag containing the 5 copies of each of the different tablets is then placed in a climatic chamber at 38 Ā° C. and 70% relative humidity for 2 weeks.

AprĆØs ces 2 semaines passĆ©es en enceinte climatique, on teste chacune des tablettes afin d'examiner l'aspect visuel et mesurer le temps de dĆ©litement de chaque type de tablette.After these two weeks spent in climate chamber, each tablet is tested to examine the visual appearance and measure the disintegration time of each type of tablet.

Les rĆ©sultats obtenus sont rĆ©capitulĆ©s dans le tableau 11 ci-dessous. Tableau 11 Tablette nĀ°8 Tablette nĀ°9 Tablette nĀ°10 Tablette nĀ°11 Tablette nĀ°12 Aspect tablette PrĆ©sence de quelques pustules et dĆ©but de lamĆ©lisation PrĆ©sence de quelques pustules et dĆ©but de lamĆ©lisation PrĆ©sence de quelques pustules et dĆ©but de lamĆ©lisation Bon aspect visuel, absence de pustules et absence de lamĆ©lisation Bon aspect visuel, absence de pustules et absence de lamĆ©lisation Temps de dĆ©litement (min:sec) 7min:40sec 8min:10sec 8min:00sec 9min:00sec 8min:55sec The results obtained are summarized in Table 11 below. <i> Table 11 </ i> Tablet n Ā° 8 Tablet n Ā° 9 Tablet n Ā° 10 Tablet n Ā° 11 Tablet n Ā° 12 Tablet appearance Presence of some pustules and beginning of lamination Presence of some pustules and beginning of lamination Presence of some pustules and beginning of lamination Good visual appearance, absence of pustules and lack of lamination Good visual appearance, absence of pustules and lack of lamination Disintegration time (min: sec) 7min: 40sec 8min: 10sec 8min: 00sec 9min: 00sec 8min: 55sec

On constate que l'aspect des tablettes nĀ°11 et nĀ°12 n'a pas Ć©tĆ© altĆ©rĆ© comparativement aux tablettes nĀ°8, nĀ°9 et nĀ°10 qui prĆ©sentent quelques pustules et un dĆ©but de lamĆ©lisation aprĆØs deux semaines en enceinte climatique. Ceci prouve que le coating intĆ©grant l'agent spĆ©cifique pour amĆ©liorer l'efficacitĆ© de rinƧage vient, de maniĆØre surprenant, amĆ©liorer la stabilitĆ© de la tablette, y compris par rapport Ć  une tablette ayant Ć©galement un coating mais qui n'inclut pas l'agent spĆ©cifique.It is noted that the appearance of tablets 11 and 12 has not been altered compared to tablets 8, 9 and 10 which have some pustules and a start of lamination after two weeks in the climatic chamber . This proves that the coating incorporating the specific agent to improve the rinsing efficiency comes, surprisingly, to improve the stability of the tablet, including with respect to a tablet also having a coating but which does not include the agent. specific.

Par ailleurs, on constate que le temps de dĆ©litement des tablettes nĀ°11 et nĀ°12 est conforme et sensiblement identique au temps de dĆ©litement des autres types de tablettes.Furthermore, it is found that the disintegration time tablets 11 and 12 is consistent and substantially identical to the disintegration time of other types of tablets.

REFERENCES BIBLIOGRAPHIQUESBIBLIOGRAPHIC REFERENCES

  • US 3,231,505US 3,231,505
  • WO 01/64829WO 01/64829
  • EP 2 196 531EP 2 196 531

Claims (17)

  1. Detergent tablet comprising a body made from compacted powder, said body being coated with a water-soluble coating, said water-soluble coating having a composition comprising a film-forming agent and water, characterised in that the composition of the water-soluble coating further comprises at least one specific agent for improving the efficiency in terms of rinsing of the detergent tablet.
  2. Detergent tablet according to claim 1, wherein the water-soluble coating has a thickness comprised between 1 Āµm and 1,000 Āµm, preferably comprised between 5 Āµm and 300 Āµm, and further preferably comprised between 15 Āµm and 150 Āµm.
  3. Detergent tablet according to any of claims 1 or 2, wherein the water-soluble coating has a weight representing between 0.5% to 15% by weight compared to the total weight of the detergent tablet, preferably between 2% to 5% by weight compared to the total weight of the detergent tablet.
  4. Detergent tablet according to any of claims 1 to 3, wherein the specific agent for improving the efficiency in terms of rinsing is an anti-spotting and/or anti-filming agent.
  5. Detergent tablet according to any of claims 1 to 4, wherein the at least one specific agent is in a proportion comprised between 0.05% and 50% by weight compared to the total weight of the composition of the water-soluble coating, preferably between 2% and 20% by weight compared to the total weight of the composition of the water-soluble coating.
  6. Detergent tablet according to any of claims 1 to 5, wherein the at least one specific agent is a polymer.
  7. Detergent tablet according to any of claims 1 to 6, wherein the at least one specific agent is selected from modified hydrophobic acrylic/styrene copolymers, or combinations thereof.
  8. Detergent tablet according to any of claims 1 to 6, wherein the at least one specific agent is selected from copolymers of acrylic acid and sulphonated monomer, copolymers of acrylic acid and sulphonic acid, copolymers of acrylic acid and maleic acid, or combinations thereof.
  9. Detergent tablet according to any of claims 1 to 6, wherein the at least one specific agent is selected from carboxylate polymers, modified hydrophobic carboxylate polymers, in particular HASE polymers, and combinations thereof.
  10. Detergent tablet according to any of claims 1 to 9, wherein the film-forming agent is in a proportion comprised between 5% and 80% by weight compared to the total weight of the composition of the water-soluble coating, preferably comprised between 20% and 60% by weight compared to the total weight of the composition of the water-soluble coating, and further preferably comprised between 30% and 55% by weight compared to the total weight of the composition of the water-soluble coating.
  11. Detergent tablet according to any of claims 1 to 10, wherein the film-forming agent is selected from polyvinyl alcohols.
  12. Detergent tablet according to claim 11, wherein the film-forming agent is selected from polyvinyl alcohols having a hydrolysis level with a molar percentage greater than or equal to 40%, preferably comprised between 70% and 98%, and further preferably comprised between 80% and 90%.
  13. Detergent tablet according to any of claims 11 or 12, wherein the film-forming agent is selected from polyvinyl alcohols having a molar mass by weight comprised between 10,000 g/mol and 200,000 g/mol, and preferably comprised between 15,000 g/mol and 100,000 g/mol.
  14. Detergent tablet according to any of claims 1 to 13, wherein the composition of the water-soluble coating further comprises a humectant.
  15. Detergent tablet according to claim 14, wherein the humectant is in a proportion less than or equal to 25% by weight compared to the total weight of the composition of the water-soluble coating, preferably in a proportion comprised between 1% and 20% by weight compared to the total weight of the composition of the water-soluble coating, further preferably in a proportion comprised between 2% and 10% by weight compared to the total weight of the composition of the water-soluble coating.
  16. Detergent tablet according to any of claims 14 or 15, wherein the humectant is selected from glycerine, polyethylene glycols, and combinations thereof.
  17. Detergent tablet according to any of claims 14 or 15, wherein the humectant is selected from polyethylene glycols having a molar mass by weight comprised between 1,000 g/mol and 4,000 g/mol.
EP16819597.2A 2015-12-04 2016-12-02 Coated detergent tablet Active EP3383989B1 (en)

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FR1561859A FR3044678B1 (en) 2015-12-04 2015-12-04 DETERGENT TABLET COATED
PCT/FR2016/053192 WO2017093694A1 (en) 2015-12-04 2016-12-02 Coated detergent tablet

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ATE189904T1 (en) * 1993-12-30 2000-03-15 Ecolab Inc STABLE HYGROSCOPIC CLEANING ITEM
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
EP0979862A1 (en) 1998-08-13 2000-02-16 The Procter & Gamble Company Multilayer detergent tablet with different hardness
US6448323B1 (en) * 1999-07-09 2002-09-10 Bpsi Holdings, Inc. Film coatings and film coating compositions based on polyvinyl alcohol
GB0004805D0 (en) 2000-03-01 2000-04-19 Procter & Gamble Solid bodies
EP1149896A1 (en) 2000-04-27 2001-10-31 The Procter & Gamble Company Coating composition for solid bodies
ATE288472T1 (en) 2000-07-31 2005-02-15 Mcbride Robert Ltd COATING OF TABLETS
DE10064985A1 (en) * 2000-12-23 2002-07-11 Henkel Kgaa Detergent tablets with coating
DE60209673T2 (en) * 2002-10-22 2006-09-21 Rohm And Haas Co. tablet coating
GB0226763D0 (en) 2002-11-15 2002-12-24 Polyval Plc Polyvinyl alcohol composition and film
US20050152855A1 (en) * 2003-09-19 2005-07-14 Damian Hajduk Materials for enhanced delivery of hydrophilic active agents in personal care formulations
EP1903099A1 (en) 2006-09-22 2008-03-26 Dalli-Werke GmbH & Co. KG Coated detergent compositions and manufacture process
EP2045319B8 (en) * 2007-09-19 2016-02-24 Dalli-Werke GmbH & Co. KG Coated detergent composition and manufacture process
ES2523029T3 (en) * 2008-12-05 2014-11-20 Dalli-Werke Gmbh & Co. Kg Polymer coated detergent tablet
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WO2017093694A1 (en) 2017-06-08
DK3383989T3 (en) 2019-06-03
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US10927330B2 (en) 2021-02-23
TR201907203T4 (en) 2019-06-21
FR3044678A1 (en) 2017-06-09

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