WO2012000914A1 - Particules pourvues d'un revêtement comportant un (co)polymère d'alcool vinylique et un polysaccharide - Google Patents

Particules pourvues d'un revêtement comportant un (co)polymère d'alcool vinylique et un polysaccharide Download PDF

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Publication number
WO2012000914A1
WO2012000914A1 PCT/EP2011/060671 EP2011060671W WO2012000914A1 WO 2012000914 A1 WO2012000914 A1 WO 2012000914A1 EP 2011060671 W EP2011060671 W EP 2011060671W WO 2012000914 A1 WO2012000914 A1 WO 2012000914A1
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WO
WIPO (PCT)
Prior art keywords
coating
polymer
glda
particle
vinyl alcohol
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Application number
PCT/EP2011/060671
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English (en)
Inventor
Cornelis Elizabeth Johannus Van Lare
Martin Heus
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Akzo Nobel Chemicals International B.V.
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Publication date
Application filed by Akzo Nobel Chemicals International B.V. filed Critical Akzo Nobel Chemicals International B.V.
Publication of WO2012000914A1 publication Critical patent/WO2012000914A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/536—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning characterised by their form or by the form of their components, e.g. encapsulated material
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/26—Gel breakers other than bacteria or enzymes

Definitions

  • the invention relates to particles of (salts of) glutamic acid ⁇ , ⁇ -diacetic acid, a chelating agent of the formula COOH-CH(-CH2-CH 2 -COOH)-N-(CH 2 -COOH)2, abbreviated as GLDA, which are coated, to processes to produce said particles, and to the use of such particles.
  • the detergent market is currently undergoing important changes. Due to ecological and regulatory reasons the use of phosphate in high concentrations in detergent formulations is to be banned altogether or must at least be greatly reduced.
  • the formulators of detergent products have to find alternatives to replace the phosphate compounds, with the most promising replacements being biodegradable chelating agents such as GLDA. Such chelating agents are used in a concentration from 5% to 60%.
  • Many detergent formulations contain (co-) builders, which are typically polymers, such as e.g. polyacrylates, phosphonates, phosphates, silicates or zeolites. These co-builders are present in formulations in a concentration from 1 % to 50%.
  • solid raw materials are required by the formulator.
  • the raw materials In for example automatic dishwashing (ADW) applications, the raw materials have to be in granule form to improve the tabletting and solids handling of the formulation. These granules typically have a size comprised between 300 and 2,000 microns.
  • the usual form in which glutamic acid N,N- diacetic acid (GLDA) and its salts are available is a liquid with an active content from 35% to 50%. After drying the substance (i.e. the powder or granules), especially when obtained in the amorphous state, shows hygroscopic properties to some extent, which makes it difficult to use for the ADW formulators.
  • the granules obtained from a granulation process are somewhat brittle and thus cannot grow easily to the required size, resulting in slow processing and lots of fines.
  • the (amorphous) chelating agent GLDA exhibits hygroscopic properties, and this will render the material sticky and thus introduce storage, handling, and manufacturing problems.
  • Flow properties of particles are critical in many ways. During manufacture of the particles themselves, they must flow smoothly relative to one another, e.g. in a fluid bed. Additionally, they must then be successfully transported to storage and transport containers. Finally, they must again be transported from storage and fed into a powder or tablet manufacturing facility. Flow problems arise due to several causes. For chelating agents, poor flow can be due to low glass transition temperatures, tackiness, wetness, and physical entanglement of multifaceted, irregularly shaped particles.
  • GLDA will move into the ADW market and likely into many other fields where a strong, green chelate is needed.
  • STPP sodium tripolyphosphate
  • NTA nitrilo triacetic acid
  • EP 884 381 discloses a mixture of GLDA, an anionic surfactant, a salt of a polymer comprising carboxylic acid units and a crystalline aluminosilicate in specific proportions.
  • EP 1803801 discloses a mixture of GLDA with at least one polyethylene glycol, a nonionic surfactant, polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene glycols or derivatives thereof.
  • mixing the chelating agent and the other additives will hardly have any beneficial effect in reducing the hygroscopic behaviour of the chelating agent.
  • the object of the invention is to provide stable coated particles of GLDA of which the hygroscopic properties are improved but also wherein GLDA is obtained in a free-flowing form so that it can be added to dry compositions and formulations that are in a powdery form.
  • Another object of the present invention is to provide a process to make coated particles of GLDA wherein a closed layer of coating is obtained while avoiding the use of very high levels of coating material.
  • another object is to provide stable coated particles of other materials that are sensitive to moisture that are relatively cheap to prepare..
  • hygroscopicity comprises two different elements, namely a time dependent element and an amount dependent element, so a hygroscopicity improvement may be both a delay in the speed/rate with which water is taken up by a material as well as a reduction of the amount of water that will be taken up by a material
  • the invention provides the use of the coated particles in detergents, agriculture, in oil field applications, in water treatment.
  • the particles are used in institutional and industrial cleaning compositions or household cleaning compositions.
  • the invention provides a method to reduce the hygroscopicity of materials by applying a coating thereon that comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide, a method to reduce the water uptake of materials by applying a coating thereon that comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide, a method to improve the flow properties of materials by applying a coating thereon that comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide, and a method to improve the chemical and/or physical stability of materials by applying a coating thereon that comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide, and to coated particles obtainable by any of these processes.
  • any and all material of which the hygroscopicity, flowability, water uptake or stability (often due to water sensitivity) is considered subject to improvement wherein such material may be a single compound or a mixture of compounds.
  • Such materials include water-sensitive compounds from the group of bleaching agents, such as percarbonates, peroxides, hypochlorites; organic molecules, such as peptides, proteins, polynucleotides; reaction initiators; catalysts; paint components, such as dyes; medicines; and pharmaceutical preparations or components.
  • the coating surrounding the GLDA chelating agent or other water-sensitive material is such that it will act to sufficiently delay the core material/chelating agent from absorbing moisture, thereby reducing the rate of particles sticking together or forming a solid mass.
  • the coating layer is sufficiently readily water-soluble to release the core material/chelating agent sufficiently rapidly in a final application wherein this is desired, this in addition without leaving a measurable amount of coating residue on the particles. Consequently, the invention provides an excellent balance between the barrier properties and the dissolution properties of the coating. Also, it was found that the coating of the invention has an improved adherence to the core and therefore the coated particles of the invention have good segregation and attrition resistance.
  • the particle once formulated will provide a stable particle size that will not change during storage or transportation (which is one element of physical stability).
  • the core material/chelating agent in the (structured) particles can be protected from the effects of UV rays, moisture, and oxygen and is therefore chemically stable. Chemical reactions between incompatible species of particles can be prevented due to the coating and the particles exhibit greatly improved storage, handling, and manufacturing properties. The flow properties thereof are improved which basically means that the material remains free flowing for a prolonged period compared to the uncoated core material/chelating agent.
  • the coated particles of the invention have a favourable ratio of ingredients that are active in their intended use on total ingredients.
  • coated particles as used throughout this application is meant to denote all particles (e.g. powder or granules) containing core material/GLDA ("the particle” or “the core”) which have been encapsulated, coated, matrix coated, or matrix encapsulated, with at least one other material (“the coating”), as a consequence of which the particles have other physical characteristics than the chelating agent without this coating.
  • Coated particles unlike plain mixtures, have more coating material on the outer side of the coated particle and more core material on the inner side of the coated particle.
  • the coating is a closed layer as established by scanning electron microscopy/EDX, which is always the case if the coating is used in an amount of at least about 30 wt% when a matrix encapsulation process is used and, if the process is a fluidized bed encapsulation process, when at least 5 wt% of coating mixture is applied on the basis of the total particle.
  • the particles can for instance have a modified colour, shape, volume, apparent density, reactivity, durability, pressure sensitivity, heat sensitivity, and photosensitivity compared to the original chelating agent.
  • the coating layer serves to improve the storage stability of the granule and to preserve flowability. This is achieved as the coating layer reduces or delays the absorption of water, i.e. reduces the hygroscopicity.
  • the GLDA-containing particle is in substantially dry form, wherein substantially dry means that the GLDA- containing particle has a water content of below 10 wt%, preferably of below 6 wt%, on the basis of (total) solids.
  • Coated particles of the invention may take several different forms depending on the processing conditions and the choice of materials.
  • Figures 1A-B depict state of the art particles that are not coated.
  • Figure 1A depicts schematically two different median particle sizes for a dried chelating agent. For example, 5-50 ⁇ particles can be made (e.g. by spray drying) or 50-500 ⁇ particles can be made (e.g. by fluid bed agglomeration).
  • Figure 1 B depicts schematically that when a structuring agent is used to provide more robust granules, the maximum size of the granules created (e.g. by fluid bed granulation) can be increased to 3,000 ⁇ .
  • FIGS 2A-C depict coated particles of this invention.
  • Figure 2A depicts the particles of this invention, where small (5-50 ⁇ ) particles are coated in a continuous matrix of coating polymer and the matrix encapsulation coating is acquired by spray drying with a high amount of coating polymer.
  • Figure 2B depicts a particle of this invention in which a set of larger chelating agent granules (or structured chelating agent granules) are coated with a thin layer of coating polymer.
  • Figure 2C e.g. depicts the coating of a large-structured granule in which an exterior polymer coating is created around an inner structured core.
  • the coated particles when making a cross-section of the coated particles they contain more than 50% of core material in the inner 50% (on the basis of the diameter) of the cross-section (which is roughly the case in the particle of Figure 2A), more preferably more than 80% (which is roughly the case in Figure 2B), and most preferably more than 90% (which is the case in Figure 2C).
  • the application of the coating material controls the particle design as e.g. shown in Figure 2, and that thus the method to apply the coating material can lead to different particles.
  • Each particle can exhibit the improved qualities of the current invention and will exhibit a number of different advantages.
  • the particle depicted schematically by Figure 2C will, due to the large particle size, need the lowest amount of coating to achieve a closed layer of coating material.
  • This particle may require the use of a structuring agent to provide a robust inner structured particle.
  • a particle more similar to Figure 2A may be created.
  • This invention also covers the use of the coated particles in detergents, agriculture, in oil field applications, in water treatment, and other applications that require or benefit from the multiple benefits provided by this invention, i.e. the dissolution of crystals/scale, the sequestration of metal ions which can otherwise lead to precipitation, and the inhibition of scale growth.
  • One preferred embodiment of this invention is the use of the coated particles in automatic dishwashing.
  • Another preferred embodiment of this invention is the use of the particles in oil well completion and production operations.
  • the vinyl alcohol (co)polymer has a melting point of more than 100°C.
  • the melting point is preferably below 300 °C.
  • the vinyl alcohol (co)polymer preferably has a Hoppler viscosity as 4% aqueous solution of 1 to 100 mPas.
  • the vinyl alcohol (co)polymer suitable as coating is often a synthetically prepared polymer.
  • the vinyl alcohol (co)polymer may be synthetically modified and besides vinyl alcohol and vinyl acetate monomers may contain other ethylenically unsaturated monomers.
  • the vinyl alcohol (co)polymer suitable as coating can be chosen from the group of (partially) hydrolyzed polyvinylacetates, (partially) hydrolyzed polyethylene- vinylacetates, or mixtures thereof.
  • the partially hydrolyzed vinyl alcohol (co)polymers and their derivatives can be modified for instance with amino groups, carboxylic acid groups and/or alkyl groups, and can have a degree of hydrolysis of preferably about 70 to 100 mol.%, in particular of about 80 to 99 mol.%, and a Hoppler viscosity in 4% aqueous solution of preferably 1 to 100 mPas, in particular of about 3 to 50 mPas (measured at 20°C in accordance with DIN 53015).
  • Other copolymerizates include styrene-maleic acid and/or vinyl ether-maleic acid copolymerizates.
  • polyvinyl alcohols with a degree of hydrolysis of 80 to 99 mol.% and a Hoppler viscosity as 4% aqueous solution of 3 to 30 mPas.
  • Suitable polysaccharides are biopolymers and their derivatives like cold water- soluble polysaccharides and polysaccharide ethers, such as for instance cellulose ethers, starch ethers (amylose and/or amylopectin and/or their derivatives), guar ethers, dextrins and/or alginates.
  • synthetic polysaccharides such as anionic, nonionic or cationic heteropolysaccharides can be used, in particular xanthan gum, welan gum and/or diutan gum.
  • the polysaccharides can be, but do not have to be, chemically modified, for instance with carboxymethyl, carboxyethyl, hydroxyethyl, hydroxypropyl, methyl, ethyl, propyl, sulfate, phosphate and/or long-chain alkyl groups.
  • Preferred usable peptides and/or proteins are for instance gelatine, casein and/or soy protein.
  • biopolymers are dextrins, starches, starch ethers, casein, soy protein, gelatine, hydroxyalkyl-cellulose and/or alkyl-hydroxyalkyl- cellulose, wherein the alkyl group may be the same or different and preferably is a Ci- to C6-group, in particular a methyl, ethyl, n-propyl- and/or i-propyl group.
  • the polysaccharide preferably is a gum like Arabic gum or xanthan gum or a cellulose ether like carboxymethylcellulose, even more preferably it is Arabic gum or carboxymethylcellulose.
  • the coating layer comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide, wherein the weight% of polysaccharide in the coating on dry basis in one embodiment is more than 0 but less than 50 wt%, preferably between 0.5 and 20 wt%, more preferably between 2 and 15 wt%, and most preferably between 3 and 12 wt%, and wherein the weight% of vinyl alcohol (co)polymer in the coating on dry basis in one embodiment is less than 100 but more than 50 wt%, preferably between 80 and 99.5 wt%, more preferably between 85 and 98 wt%, and most preferably between 88 and 97 wt%.
  • the coated particles of the invention may contain other components besides the at least one polysaccharide and vinyl alcohol (co)polymer component in the coating, like for example a low amount (i.e. less than 30 wt%, preferably less than 20 wt%, more preferably less than 10 wt% on total coating) of another water-soluble polymer.
  • the coating may contain two or more polysaccharides and/or two or more vinyl alcohol (co)polymers.
  • the coating may be applied in two or more coating layers that may be the same or different in their composition, though it is preferred to apply a mixture of vinyl alcohol (co)polymer and polysaccharide to give one coating layer comprising both ingredients.
  • one embodiment may have the polysaccharide in one layer and the vinyl alcohol (co)polymer in another layer. In such event it is preferred to have (more of) the polysaccharide in a layer closer to the core than the vinyl alcohol (co)polymer and most preferred to have (more of) the vinyl alcohol (co)polymer in the outer layer applied on the particle.
  • the outer layer of the coating preferably comprises the at least one vinyl alcohol (co)polymer and the polysaccharide.
  • one of the coating layers may contain a compound that is functional in the end application of the particle (i.e. "functional additives").
  • the inner coating more preferably contains a scale inhibitor or another building compound/chelating agent (citrate, MGDA), a pH buffer (sodium carbonate or silicate) or a hydrophobic polymer.
  • a scale inhibitor or another building compound/chelating agent citrate, MGDA
  • a pH buffer sodium carbonate or silicate
  • a hydrophobic polymer is another preferred embodiment wherein an inner coating contains a salt and an outer coating comprises at least one vinyl alcohol (co)polymer and at least one polysaccharide.
  • the inner coating layer comprises a salt that is functional in the detergent composition such as sodium carbonate, sodium citrate or sodium silicate.
  • the inner coating in addition contains a water-soluble polymer, a polysaccharide or a scale-inhibiting polymer.
  • an additional outer layer may be applied on the coated particles, which may comprise a flowing aid such as fumed silica.
  • the coated particles of the invention in addition to GLDA may contain another chelating agent, such as for example methylglycine ⁇ , ⁇ -diacetic acid (MGDA), ethylenediamine ⁇ , ⁇ , ⁇ ', ⁇ '- tetraacetic acid (EDTA), N-hydroxyethyl ethylenediamine ⁇ , ⁇ ', ⁇ '-triacetic acid (HEDTA), diethylenetriamine penta acetic acid (DTPA), or a salt of any of these agents.
  • MGDA methylglycine ⁇ , ⁇ -diacetic acid
  • EDTA ethylenediamine ⁇ , ⁇ , ⁇ ', ⁇ '- tetraacetic acid
  • HEDTA N-hydroxyethyl ethylenediamine ⁇ , ⁇ ', ⁇ '-triacetic acid
  • DTPA diethylenetriamine penta acetic acid
  • This further chelating agent may be present in the core or in the coating.
  • the particle (core) of the invention may comprise further functional additives that can be chosen from the group of scale-inhibiting additives, structurants, (co)builders, and pH buffers.
  • the core will contain a (co)builder as a further additive.
  • the core is structured with a suitable structurant. Accordingly, the particles of the invention may optionally comprise structurants which improve the physical strength of the particle.
  • the (co)builder can include several salts and/or inorganic additives which contribute to the strength of the resulting particles and which also function as sequestration materials or as builders.
  • the building salts found to be functional as a structurant for the chelating agents are citrate, carbonate, silicate, and sulfate salts.
  • the sodium salts of materials are used.
  • sodium carbonate, sodium citrate, and sodium silicate are preferred due to their functionality (e.g. as a scale-inhibiting additive).
  • inorganic (nano-) particles, such as silica can be used.
  • the coating layer(s) may comprise further functional additives that can be chosen from the group of scale-inhibiting additives, structurants, (co)builders, nanoparticles, and pH buffers.
  • Examples of functional additives are salts like citrate, silicate, glycolate, oxalate, lactate, succinate, malonate, maleate, diglycolate, fumarate, stearate, chloride, nitrate, percarbonate or carbonate salt, such as the alkali metal salt of any of these, that besides their above-indicated functionality have a pH buffering effect as well, chelating agents or scale-inhibiting polymers.
  • Scale-inhibiting polymers can have a variety of chemical forms and are specifically selected from synthetic, natural, and hybrid scale-inhibiting polymers.
  • the synthetic polymer includes selected levels of carboxylation, sulfonation, phosphorylation, and hydrophobicity to give good film forming and humidity resistance as well as good co-building and crystal growth inhibition properties.
  • the natural polymers are likewise prepared with a combination of molecular weight modification, carboxylation, sulfonation, phosphorylation, and hydrophobic properties to give good co-building and crystal growth inhibition properties.
  • the hybrid polymers combine natural and synthetic monomers and polymers to give good co- building and crystal growth inhibition properties.
  • scale-inhibiting polymers and/or salts as an additive is that these materials can be or are already used as co-builder or pH buffer in most detergent formulations and will therefore have a beneficial effect during the wash. Therefore, the current invention gives a superior product which provides other benefits such as co-builder or crystal growth inhibition. Also, such particles of the present invention have excellent flow properties.
  • the (structured) particles have many useful functions and can be employed in many different areas, frequently connected with applications in which the chelating agent contents of the particle have to be released into the surrounding environment under controlled conditions.
  • the amount of GLDA in the coated particle in an embodiment is at least 30 wt%, more preferably at least 50 wt %, even more preferably at least 60 wt%, most preferably at least 90 wt%, and up to 95 wt% on basis of the total weight of the particle.
  • the coated particles of the invention in one embodiment contain 15 to 95 wt% of the GLDA and optionally other chelating agents, 5 to 85 wt% of the coating, and 0 to 40 wt% of further additives. In a preferred embodiment, they contain 30 to 95 wt% of the GLDA and optionally other chelating agents, 5 to 50 wt% of the coating, and 0 to 20 wt% of further additives.
  • the coated particles contain 60-95 wt% of GLDA and optionally other chelating agents, 5 to 20 wt% of the coating and 0 to 20 wt% of further additives, the total amounts of ingredients adding up to 100 wt%.
  • the particle comprises HnYm-GLDA, wherein m is at least 1 and n is at most 3.
  • particles wherein the values of m and n are different can also be used.
  • other components in the particle or in the coating may exchange protons with the GLDA (i.e. accept therefrom or provide thereto), ensuring that effectively the desired number of hydrogen atoms are exchangeably available per GLDA anion.
  • m is 1 .5 - 3.8, most preferably m is 2.5 - 3.6.
  • the particles of the invention in one embodiment have a particle size of 200 to 2,000 microns ( ⁇ ), most preferably 500 - 1 ,000 microns.
  • the coating layer contains at least one vinyl alcohol (co)polymer and at least one polysaccharide comprises the steps of mixing the at least one vinyl alcohol (
  • the process involves a step preceding applying the coating mixture or the vinyl alcohol (co)polymer and the polysaccharide at least partly one after the other on the particle, wherein a salt layer is applied on the particle, preferably a citrate, silicate, glycolate, oxalate, lactate, succinate, malonate, maleate, diglycolate, fumarate, stearate, chloride, nitrate, percarbonate or carbonate salt.
  • a salt layer is applied on the particle, preferably a citrate, silicate, glycolate, oxalate, lactate, succinate, malonate, maleate, diglycolate, fumarate, stearate, chloride, nitrate, percarbonate or carbonate salt.
  • Suitable processes to apply the coating on the particle in accordance with the process of the invention are for example disclosed in the Kirk Othmer Encyclopedia of Chemical Technology, Vol 16, Microencapsulation pages 438 - 463 by C.Thies; John Wiley & Sons Inc. 2001 )) and include but are not limited to the following processes:
  • Fluidized-bed encapsulation technology which involves spraying shell material in solution or hot melt form onto solid particles suspended in a stream of heated gas, usually air. Although several types of fluidized-bed units exist, so-called top and bottom spray units are used most often to produce microcapsules.
  • top-spray units hot melt shell materials are sprayed onto the top of a fluidized-bed of solid particles.
  • the coated particles are subsequently cooled producing particles with a solid shell.
  • This technology is used to prepare a variety of encapsulated ingredients.
  • bottom-spray or Wurster units the coating material is sprayed as a solution into the bottom of a column of fluidized particles.
  • the freshly coated particles are carried away from the nozzle by the airstream and up into the coating chamber where the coating solidifies due to evaporation of solvent.
  • the particles settle. They ultimately fall back to the bottom of the chamber where they are guided once again by the airstream past the spray nozzle and up into the coating chamber.
  • Coating uniformity and final coated particle size are strongly influenced by the nozzle(s) used to apply the coating formulation.
  • This technology is routinely used to encapsulate solids, especially pharmaceuticals (qv). It can coat a wide variety of particles, including irregularly shaped particles.
  • the technology generally produces capsules >100 - 150 micrometer, but can produce coated particles ⁇ 100 micrometer.”
  • the coated particles are prepared by spraying the coating onto the particle using a fluid bed coating process as for example described by E. Teunou, D. Poncelet, "Batch and continuous fluid bed coating review and state of the art," J. Food Eng. 53 (2002), 325 - 340.
  • the fluidized bed is a tank with a porous bottom plate. The plenum below the porous plate supplies low pressure air uniformly across the plate leading to fluidization.
  • the process comprises the following steps:
  • a compound to be encapsulated in the form of a powder is fluidized with air at an air inlet temperature below the melting temperature of the powder;
  • a coating liquid comprising a water based coating solution is sprayed onto the powder via a nozzle, followed by subsequent evaporation of the water by using elevated temperatures in the fluid bed. This leaves behind a coating layer on the particles with the compound in the core.
  • the process of the present invention may involve a preceding step of preparing the particle (containing GLDA) on which in a subsequent step the coating mixture is applied.
  • the particle can be made by drying a solution of the core material/GLDA and the optional further additives. Drying the solution can be done by any drying method known to the person skilled in the art, like evaporating off the water via e.g. spray drying, fluid bed spray drying, fluid bed granulation.
  • the dry material may optionally be further processed, for example by compacting and/or crushing the material until it has the desired shape, i.e. is in the form of core particles of the desired size.
  • the step of compacting includes any method wherein the particles are agglomerated by applying an external force on them, for instance by extruding, tabletting or agglomerating them under a pressure of suitably from 40 to 200 MPa, preferably a pressure of from 50 to 120 MPa, most preferably of from 75 to 100 MPa.
  • the pressure used for compacting the material is the pressure applied at uniaxial compaction of a tablet (leading to a certain density of the compacted particle mixture).
  • compacting may suitably be done by other compactors, like a roll compactor.
  • the pressure to be used is the pressure that results in the same density of the compact as in uniaxial compaction.
  • the step of crushing includes any method whereby the size of the particles is decreased and is intended to include methods like breaking, crushing, or milling.
  • the coating mixture layer is applied on the material containing the chelating agent at a pH of 2 -1 1 , more preferably 5-10, most preferably 7 - 10.
  • the process to prepare the coated particles encompasses the preparation of a granule that is subsequently coated in a fluid bed coating process.
  • the granule preparation is started by dissolving the chelating agent in water together with the coating material and if required a structurant. This mixture is sprayed into a hot spray drying chamber leading to the evaporation of water.
  • the particles formed this way are recirculated in the spray chamber and at the same time spraying the water based mixture into the chamber is continued, due to which the particle grows and a granule is gradually formed.
  • the composition gradient inside the granule can be modified by altering the composition of the spray mix while spraying it into the drying chamber.
  • the particle formed is described as a co- granule as it consists of the compound, the coating material, and, if required, a structurant.
  • the obtained co-granule is subsequently coated in a fluid bed process.
  • a powder is fluidized with warm air and a water based coating solution is sprayed onto the powder.
  • the water is evaporated, leaving a coating on the particle surface.
  • the amount of coating can be controlled easily by manipulating the spray on time and spray mix composition. To control the coating quality, it may be necessary to increase the temperature of the coating solution (i.e. spray mix). This will lower the spray mix viscosity, most likely leading to a better atomization and droplet formation which gives a better distribution of the coating material on the granule.
  • Co-granules of GLDA and Alcoguard 4160 were produced in a spray granulation process.
  • the co-granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S available from Akzo Nobel Functional Chemicals LLC, Chicago, IL, USA) and the anti-scaling polymer Alcoguard 4160 (available as a dissolved polymer solution or in dry form from AkzoNobel Surface Chemistry LLC, Chicago, IL, USA).
  • GL47S and GL-Na-36S were mixed with Alcoguard 4160 (also abbreviated as "4160"), where the ratio of the total amounts of GLDA and Alcoguard 4160 was 80:20 in weight.
  • Alcoguard 4160 also abbreviated as "4160”
  • This mixture was sprayed into a hot spray drying chamber, leading to the evaporation of water.
  • the particles formed this way were recirculated into the spray chamber via cyclones and at the same time spraying the water based GLDA 4160 mixture into the chamber was continued, due to which the particle grew and a granule was gradually formed.
  • the mixture of GLDA and 4160 was continuously sprayed into a fluid bed spray granulator type AGT, equipped with cyclones, an external filter unit, and a scrubber.
  • the air flow was kept between 700 - 1 ,300 m 3 /hour and air inlet temperatures between 100 and 250°C were used.
  • the particle formed is described as a co-granule, as it consisted of GLDA and the anti- scaling polymer. This process resulted in a free flowing powder, described as "uncoated" co-granule.
  • the same process as described for the co- granule was used, except that in this case the spray mix consisted of GL-47-S and GL-Na-36S mixed in a ratio of 85:15 wt%, hence no anti-scaling polymer was used in the particle preparation.
  • the "uncoated" GLDA 4160 co-granule or GLDA-pure granule was subsequently coated in a fluid bed (GEA Aeromatic Strea-1 ) using a Wurster set-up and a two-fluid nozzle.
  • the Wurster set-up is a draft tube positioned in the centre of the fluid bed, below which a nozzle is positioned that sprays fine droplets upwards into the tube. These droplets hit the granule surface and after drying leave behind some dry coating material. Using this set-up an even coating can be applied.
  • the air inlet temperature used was 80 - 90°C.
  • the air flow was chosen such that visually an even fluidization was obtained, which implies a setting between 10 and 80% of the maximum air flow on the GEA Aeromatic Strea-1 .
  • the spray-on rate of the coating solution was chosen such that an even coating was obtained on the particles giving no particle aggregation (i.e. about 0.5 - 1 gram/minute), resulting in a particle coated with an even coating layer. Coating was continued until a predefined amount of coating was obtained on the particles.
  • a Glatt laboratory fluid bed was used. In this equipment the air inlet temperatures were varied between 80 C and 150°C and where not specified in below Examples a temperature of about 100°C was used. Spraying of the liquid was done via top spray using a twin fluid air assisted nozzle. Again, the spray rate was chosen such that aggregation was avoided and an even coating was obtained.
  • the resulting powders were poured in a 1 -particle thick layer onto a petri dish and stored in a climate chamber operated at 16°C and 60% Relative Humidity.
  • the weight increase as a function of time was measured, as a measure for the rate of absorption of moisture.
  • the weight increase was recomputed into a % weight increase by using the following formula:
  • the fiowabiiity of a powder was determined by manually moving the petri dish stored in the climate chamber and visually estimating the number fraction of particles that did not stick to the dish but moved freely. Hence a fiowabiiity figure (%ff) of 100% means that all particles moved freely, a figure of 0% means that all particles were sticking completely to the dish. Flowability is considered to be acceptable when at least about 90% of the particles move freely.
  • the melting temperature was measured using a Differential Scanning Calorimeter (make Mettler Toledo).
  • the three types tested were Mowiol 3-85, Mowiol 4-88 (both ex Kuraray Europe GmbH), and Elvanol 71 -30 (ex DuPont). The powders were used as such. All three types showed similar results, with a glass transition temperature between 38 and 45°C and a melting temperature between about 160 and 190°C.
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), Arabic gum (laboratory grade, ex Acros Organics), anti-scaling polymer Alcoguard 4160, and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • Arabic gum laboratory grade, ex Acros Organics
  • anti-scaling polymer Alcoguard 4160 anti-scaling polymer Alcoguard 4160
  • the water-soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • a co-granule of GLDA and Alcoguard 4160 was produced in a spray granulation process using the process as described above.
  • the "uncoated" GLDA 4160 co-granule was subsequently coated with mixtures of Mowiol 3-85 and Arabic gum in a fluid bed (GEA Aeromatic Strea-1 ).
  • the Mowiol 3-85 was dissolved in water to give a 16 wt% solution and Arabic gum powder was added, with the Mowiol/gum ratio being varied.
  • the levels of Arabic gum (based on Mowiol 3-85 on dry basis) were: 0, 0.5, 2, 5, 10, 20, 50, and 100%.
  • the powders were stored at 16°C, 60% RH in a climate chamber and the moisture absorption was determined. From these curves, the time to reach a weight increase of 10wt% was determined. The time to reach 10 wt% as a function of the level of Arabic gum is given below in Table 1 and is graphically shown in Figure 3.
  • Table 1 and Figure 3 show that the Arabic gum has a synergistic effect on the Mowiol coating. By adding an optimal amount of gum to the polyvinyl alcohol the moisture barrier properties are significantly improved, with an optimum value being found.
  • Figure 3 shows that a preferred level for Arabic gum in the coating layer is about 10% (based on polyvinyl alcohol on dry basis).
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), anti-scaling polymer Alcoguard 4160, carboxy methyl cellulose (CMC) AF0305 (ex AkzoNobel Cellulosic Specialties), and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • anti-scaling polymer Alcoguard 4160 anti-scaling polymer Alcoguard 4160
  • CMC carboxy methyl cellulose
  • AF0305 ex AkzoNobel Cellulosic Specialties
  • water-soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • a co-granule of GLDA and Alcoguard 4160 was produced in a spray granulation process using the process as described above.
  • the "uncoated" GLDA 4160 co-granule was subsequently coated with mixtures of Mowiol 3-85 and CMC in a fluid bed (GEA Aeromatic Strea-1 ).
  • the Mowiol 3-85 was dissolved in water and a pre-made CMC solution powder was added, with the Mowiol/CMC ratio being varied.
  • the levels of CMC AF0305 (based on Mowiol 3-85 on dry basis) were: 0, 1 , 2, 5, 7, 10, and 50%.
  • the powders were stored at 16°C, 60% RH in a climate chamber and the moisture absorption was determined. From these curves, the time to reach a weight increase of 5wt% was determined. The time to reach 5 wt% as a function of the level of CMC AF0305 is given below in Table 2 and is graphically shown in Figure 4.
  • Figure 4 and Table 2 show that the CMC has a synergistic effect on the Mowiol coating. By adding CMC to the polyvinyl alcohol the moisture barrier properties are significantly improved.
  • Figure 4 shows that a preferred level for CMC in the coating layer is about 5wt% (based on polyvinyl alcohol on dry basis).
  • Example 3 Effect of other polysaccharides in polyvinyl alcohol coating
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), anti-scaling polymer Alcoguard 4160, the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH) and various polysaccharides. The following polysaccharides were selected:
  • CMC Carboxy methyl cellulose
  • CMC Carboxy methyl cellulose
  • a co-granule of GLDA and Alcoguard 4160 was produced in a spray granulation process using the process as described above.
  • the "uncoated" GLDA 4160 co-granule was subsequently coated with mixtures of Mowiol 3-85 and a polysaccharide selected from the list above in a fluid bed (GEA Aeromatic Strea-1 ).
  • the Mowiol 3-85 was dissolved in water and the polysaccharide powder was added, with the Mowiol/polysaccharide ratio being set at 98:2 or 90:10.
  • PVOH polyvinyl alcohol
  • the powders were stored at 16°C, 60% RH in a climate chamber and the moisture absorption was determined. From these curves, the time to reach a weight increase of 5 wt% was determined. The table below gives the time to reach 5 wt% increase for the various PVOH/polysaccharide combinations. This table shows that all polysaccharides give improved moisture barrier properties of the coating when compared to the Mowiol 3-85 only coating. Below, Table 3 shows that polysaccharides have a positive synergistic effect on the barrier properties for polyvinyl alcohol.
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), Arabic gum (laboratory grade, ex Acros Organics), anti-scaling polymer Alcoguard 4160, and the water-soluble polymers polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH), polyvinyl pyrrolidone PVP Luvitec VA64 (available from BASF), and polyethylene glycol PEG6000 (available as laboratory grade from Fluka).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • Arabic gum laboratory grade, ex Acros Organics
  • anti-scaling polymer Alcoguard 4160 and the water-soluble polymers polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH), polyvinyl pyrrolidone PVP Luvitec VA64 (available from BASF), and polyethylene glycol PEG6000 (available as laboratory grade from Fluka).
  • the "uncoated" GLDA 4160 co-granule was subsequently coated with in total 10wt% of a mixture containing polymer and Arabic gum in a ratio 90:10 in a fluid bed (GEA Aeromatic Strea-1 ). All polymers were dissolved in water to which the Arabic gum was added and dissolved and these mixtures were sprayed onto the GLDA co-granule in the fluid bed Aeromatic coater, until 10 wt% of that mixture was coated onto the co-granule.
  • the powders were stored at 16°C, 60% RH in a climate chamber and the moisture absorption was determined. The results are shown below in Table 4 and Figure 5 and the results for the PVP and PEG6000 alone are also given.
  • VA64 gum [90:10] PEG6000 gum [90:10] dT [hrs] wt% water wt% water wt% water wt% water wt% water
  • Table 4 and Figure 5 show that the Arabic gum addition has no significant positive effect on improving the moisture barrier properties for PVP and PEG6000. For the PEG6000 if anything, it has even a negative effect.
  • Example 5 Citrate with Arabic gum and level of Mowiol needed for flowabilitv of co-granules
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), anti-scaling polymer Alcoguard 4160, the functional salt tri- sodium citrate (laboratory grade, ex Fisher Scientific), Arabic gum (laboratory grade, ex Acros Organics), and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • anti-scaling polymer Alcoguard 4160 the functional salt tri- sodium citrate
  • Arabic gum laboratory grade, ex Acros Organics
  • water-soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • First co-granules of GLDA and Alcoguard 4160 were produced in a spray granulation process using the same process as described before.
  • the "uncoated" GLDA 4160 co-granule was subsequently coated with a mixture of citrate and Arabic gum in a Glatt batch fluid bed. This was done using a solution in water with tri-sodium citrate and Arabic gum, where the ratio citrate/gum was about 99:1 .
  • This solution was coated onto the co-granules, using a top spray two-fluid nozzle, until about 10 wt% citrate/gum was coated onto the co-granule.
  • the co-granule coated with citrate was subsequently coated in the Glatt fluid bed coater with Mowiol 3-85/Arabic gum in a ratio 90:10wt%.
  • the uncoated co-granule has a flowability of 0% within about 1 hour.
  • Figure 6 and Table 5 show that using citrate/Arabic gum gives a significant reduction in moisture uptake.
  • Figure 6 also shows that the more PVOH/gum is used, the slower the moisture absorption.
  • Example 6 Citrate with Arabic gum and level of Mowiol needed for flowability of GLDA pure granules
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), the functional salt tri-sodium citrate (laboratory grade, ex Fisher Scientific), Arabic gum (laboratory grade, ex Acros Organics), and the water- soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • the functional salt tri-sodium citrate laboratory grade, ex Fisher Scientific
  • Arabic gum laboratory grade, ex Acros Organics
  • water- soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • First granules of GLDA were produced in a spray granulation process using the same process as described before.
  • the "uncoated" GLDA granule was subsequently coated with a mixture of citrate and Arabic gum in a batch fluid bed (make Glatt). This was done using a solution in water with tri-sodium citrate and Arabic gum, where the ratio citrate/gum was about 99:1 .
  • This solution was coated onto the granules, using a top spray two-fluid nozzle, until about 10 wt% citrate/gum was coated onto the co-granule.
  • the GLDA granule coated with citrate was subsequently coated in the Glatt fluid bed coater with Mowiol 3-85/gum in a ratio of 90:10.
  • Table 6 and Figure 7 show that for the GLDA granule a citrate layer gives a reduction in moisture absorption (when compared to the uncoated GLDA granules as shown in Example 5), but that the flowability is subject to improvement after just 1 hour of storage at 16°C, 60% Relative Humidity.
  • Table 6 shows that for the GLDA granule pre-coated with citrate/gum, already 5% Mowiol/gum is sufficient to obtain an acceptable flowability for over 48 hours after storage at 16°C, 60% Relative Humidity. When the Mowiol/gum level is raised to 10 wt%, moisture absorption is further delayed and flowability is further improved.
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), functional salts, Arabic gum (laboratory grade, ex Acros Organics) and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • the salts used were selected based on their functionality in dishwashing applications and included tri-sodium citrate (laboratory grade, ex Fisher Scientific), sodium carbonate anhydrous (laboratory grade, ex J.T. Baker), and sodium silicate H265HP (ex PQ Europe, PQ Nederland bv).
  • GL-47-S and GL-NA-36-S were mixed in a ratio of 85:15.
  • the "uncoated" GLDA granule was subsequently coated with the salts in a fluid bed (GEA Aeromatic Strea-1 ).
  • the salts were dissolved in water and Arabic gum was added, such that the salt/gum ratio was about 99:1 .
  • This mixture was sprayed onto the GLDA granule in the fluid bed Aeromatic coater.
  • an additional polyvinyl alcohol layer was coated on, using a 16 wt% solution of Mowiol 3-85 and gum, with the Mowiol/gum ratio being 90:10.
  • the solutions were all coated onto the co-granules, using the Aeromatic Strea-1 fluid bed coater with a Wurster set-up and a two-fluid nozzle.
  • the air inlet temperature used was 80°C.
  • the following compositions were prepared using aqueous solutions of the salts, Arabic gum, and Mowiol 3-85:
  • the resulting powders were all stored in a climate chamber operated at 16°C and 60% Relative Humidity.
  • the results of the moisture absorption measurements are given below in Table 7 and Figure 8.
  • the table also shows as a reference the moisture uptake of the uncoated GLDA granule.
  • Figure 8 and Table 7 show that the use of a coating that consists of a functional salt followed by a coating of Mowiol 3-85 and a polysaccharide gives a reduction in moisture uptake.
  • This exemplifies that various functional (in-) organic salts and combinations thereof can advantageously be used as an intermediate coating layer.
  • Example 8 Sodium silicate as intermediate layer
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), the anti-scaling polymer Alcoguard 4160, sodium silicate Crystal0265 (ex PQ Corporation, Netherlands), Arabic gum (laboratory grade, ex Acros Organics), and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • Alcoguard 4160 sodium silicate Crystal0265
  • Arabic gum laboratory grade, ex Acros Organics
  • water-soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • Table 8 and Figure 9 show that adding a layer of sodium silicate using the process condtions of this Example only gives a reduction in the rate of moisture absorption. However, flowability of those granules can be considered still insufficient. Applying a coating with Mowiol 3-85/gum gives a further significant improvement in moisture absorption and the flowability remains acceptable for at least 24 hours for the two levels of sodium silicate that were used, i.e. 13 wt% and 20 wt%.
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), the anti-scaling polymer Alcoguard 4160, the functional salt tri- sodium citrate (laboratory grade, ex Fisher Scientific), Arabic gum (laboratory grade, ex Acros Organics), and the water-soluble polyvinyl-alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • the anti-scaling polymer Alcoguard 4160 the functional salt tri- sodium citrate
  • Arabic gum laboratory grade, ex Acros Organics
  • water-soluble polyvinyl-alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • the "uncoated" GLDA 4160/citrate co-granule was subsequently coated with Mowiol 3-85 and Arabic gum in a fluid bed (Glatt lab scale) by using a 6% solution of Mowiol 3-85/Arabic gum, with the ratio of Mowiol 3-85 and Arabic gum being 90:10.
  • This solution was coated onto the co-granules, using a top spray two-fluid nozzle, until about 10wt% of the Mowiol/Arabic gum was coated onto the co-granule.
  • Table 9 and Figure 10 show that it is possible to generate a three-compound co-granule.
  • the co-granule as such absorbs moisture fast.
  • 10 wt% Mowiol/Arabic gum is used, the rate of moisture absorption is significantly reduced and flowability is acceptable for at least the first 6 hours of storage at 16°C, 60% RH.
  • Table 9 Results of moisture absorption and flowability (%ff)
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), tri-sodium citrate (laboratory grade, ex Fisher Scientific), Arabic gum (laboratory grade, ex Acros Organics), and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • tri-sodium citrate laboratory grade, ex Fisher Scientific
  • Arabic gum laboratory grade, ex Acros Organics
  • Mowiol 3-85 available from Kuraray Europe GmbH
  • the "uncoated" GLDA granule was subsequently coated with a layer of citrate/Arabic gum and subsequently with a layer of Mowiol/gum in a fluid bed (GEA Aeromatic Strea-1 ).
  • a layer of citrate/Arabic gum subsequently with a layer of Mowiol/gum in a fluid bed (GEA Aeromatic Strea-1 ).
  • the citrate was dissolved in water and Arabic gum was added in two levels, such that the citrate/gum ratio in the final coating was about 99:1 and 83:17.
  • These mixtures were sprayed onto the GLDA granule in the fluid bed Aeromatic coater until about 15wt% of citrate/gum coating was achieved.
  • Table 10 and Figure 1 1 show that both gum levels in the citrate layer give similar results, with the higher gum level of about 17% (based on dry basis for the citrate/gum layer) giving the largest reduction in the rate of moisture absorption.
  • Example 11 Incorporation of anti-scaling polymer via co-granule or as coating layer
  • Granules were made on the basis of GLDA (Dissolvine GL-47-S and Dissolvine GL-Na-36-S), the anti-scaling polymer Alcoguard 4160, the functional salt tri- sodium citrate (laboratory grade, ex Fisher Scientific), Arabic gum (laboratory grade, ex Acros Organics), and the water-soluble polyvinyl alcohol Mowiol 3-85 (available from Kuraray Europe GmbH).
  • GLDA Dissolvine GL-47-S and Dissolvine GL-Na-36-S
  • the anti-scaling polymer Alcoguard 4160 the functional salt tri- sodium citrate
  • Arabic gum laboratory grade, ex Acros Organics
  • water-soluble polyvinyl alcohol Mowiol 3-85 available from Kuraray Europe GmbH.
  • the GLDA 4160 co-granules were subsequently coated with 10 wt% citrate/gum, with a citrate/gum ratio of about 99:1 and thereafter the granules were coated with 5 wt% and 10 wt% Mowiol/gum, with the Mowiol/gum ratio being [90:10]. This was all done in a lab scale Glatt fluid bed coater using a top spray two-fluid nozzle.
  • the GLDA pure granules were coated with 20 wt% Alcoguard 4160, to get the same composition as the GLDA/4160 co-granule. This is denoted by GLDA-G + 20% 4160.
  • This coating was done in a lab scale Glatt fluid bed coater using a top spray two-fluid nozzle and the Alcoguard 4160 solution, as is, which has a solids content of about 41 %.
  • the GLDA-G + 20% 4160 granules were subsequently coated with 10 wt% citrate/gum, with a citrate/gum ratio of about 99:1 and after that the granules were coated with 5 wt% and 10 wt% Mowiol/gum, with the Mowiol/gum ratio being [90:10]. This was all done in a lab scale Glatt fluid bed coater using a top spray two-fluid nozzle.

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Abstract

La présente invention concerne une particule revêtue contenant une particule et un revêtement, la particule contenant de l'acide N,N-diacétique d'acide glutamique ou l'un de ses sels partiels de formule HnYm-GLDA, Y étant un cation choisi dans le groupe comprenant le sodium, le potassium et leurs mélanges, et n + m = 4. Le revêtement contient au moins un (co)polymère d'alcool vinylique et au moins un polysaccharide. L'invention concerne également un procédé de préparation de cette particule et son utilisation. En outre, l'invention concerne un procédé permettant de réduire le caractère hygroscopique et l'absorption d'eau et/ou d'améliorer la stabilité et les propriétés d'écoulement de matériaux.
PCT/EP2011/060671 2010-06-28 2011-06-27 Particules pourvues d'un revêtement comportant un (co)polymère d'alcool vinylique et un polysaccharide WO2012000914A1 (fr)

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JP2020100830A (ja) * 2014-02-13 2020-07-02 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 粉末及び顆粒、この粉末及び顆粒の製造方法、並びに、その使用方法
US11518965B2 (en) 2014-02-13 2022-12-06 Basf Se Powder and granule, process for making such powder and granule, and use thereof
EP3050947A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Emballage de détergent
WO2016126582A1 (fr) * 2015-02-02 2016-08-11 The Procter & Gamble Company Emballage de détergent
US10047323B2 (en) 2015-02-02 2018-08-14 The Procter & Gamble Company Detergent composition comprising MGDA and a sulfonated copolymer
WO2019162135A1 (fr) * 2018-02-23 2019-08-29 Unilever N.V. Procédé de préparation d'une composition solide comprenant un aminopolycarboxylate
WO2019162136A1 (fr) * 2018-02-23 2019-08-29 Unilever N.V. Composition solide détergente comprenant un aminopolycarboxylate et un acide organique
CN111757925A (zh) * 2018-02-23 2020-10-09 荷兰联合利华有限公司 制备包含氨基多羧酸盐的固体组合物的方法
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