WO2015038597A1 - Agent oxydant encapsulé ayant une libération retardée contrôlée - Google Patents

Agent oxydant encapsulé ayant une libération retardée contrôlée Download PDF

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Publication number
WO2015038597A1
WO2015038597A1 PCT/US2014/054931 US2014054931W WO2015038597A1 WO 2015038597 A1 WO2015038597 A1 WO 2015038597A1 US 2014054931 W US2014054931 W US 2014054931W WO 2015038597 A1 WO2015038597 A1 WO 2015038597A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxidizing agent
coating
coating layer
encapsulated
agent according
Prior art date
Application number
PCT/US2014/054931
Other languages
English (en)
Inventor
Janet AKANDE
Michael J. Unhoch
Original Assignee
Arch Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arch Chemicals, Inc. filed Critical Arch Chemicals, Inc.
Publication of WO2015038597A1 publication Critical patent/WO2015038597A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • the present invention relates to an oxidizing agent which is coated or encapsulated with a coating layer.
  • the oxidizing agent is released from the encapsulating coating after a period of time, which introduces the oxidizing agent into the desired use environment.
  • this form tends to be incompatible with other common laundry additive materials such as enzymes, polymers, surfactants, color additives such as dyes, brighteners, and fragrance additives as the chlorine will interact with these materials so as to reduce their effectiveness.
  • sodium hypochlorite tends to stain and/or remove color if spilled or splashed onto the fabric.
  • this form of free chlorine at typical addition levels can result in fabric damage over time with repeated usage.
  • Calcium hypochlorite is known for its bleaching properties and efforts are on the way to make calcium hypochlorite a product useable in the laundry and other applications.
  • calcium hypochlorite is well known to be unstable in the presence of organic materials, such as hydrocarbon fluids, glycerol and the like.
  • One solution to making calcium hypochlorite stable is to coat or encapsulate the calcium hypochlorite with layers of materials.
  • the present invention provides an encapsulated oxidizing agent having: a) a core having an outer surface, the core being formed from a composition comprising at least one oxidizing agent; and b) a first coating layer applied to the outer surface of the core, the coating containing as a predominate component of the coating, an alkali metal salt, a multivalent metal salt or hydroxide wherein the coating completely covers the outer surface of the core.
  • the encapsulated oxidizing agent is calcium hypochlorite, trichloroisocyanuric acid (TCCA), sodium
  • SDCC dichloroisocyanurate
  • chloro hydantoins bromo hydantoins or a mixtures thereof.
  • the encapsulated oxidizing agent is provide with a second coating layer, the second coating layer being applied over the first coating layer.
  • the second coating layer serves to provide the release profile of the oxidizing agent from the encapsulating coatings. Additional coating layers may be further applied to the second or any subsequent coating layers.
  • encapsulated oxidizing agent having a core having an outer surface, the core being formed from a composition being at least one oxidizing agent. Covering this core is a first coating layer applied to the outer surface of the core, the first coating layer completely covers the outer surface of the core and the first coating layer has a thickness of 0.5 to 5 microns.
  • the oxidizing agent is calcium hypochlorite
  • the first coating layer is predominately calcium hydroxide
  • the second coating layer is sodium silicate
  • the composition is useable as whitening additive for laundry detergents, as a whitening additive for automatic laundry machines, as a toilet bowl cleaner, as sanitizing additive for an automatic dishwashing machine, as a chlorination additive for pools and spas and the like.
  • the present invention provides an encapsulated disinfecting or sanitizing agent, which is coated with one or more layers of one or more coating compositions, where the coating compositions encapsulate the disinfecting or sanitizing agents.
  • the sanitizing or disinfecting agent is an oxidizing agent. It has been surprisingly discovered that the oxidizing agent encapsulated as described herein, can be made to control the release of the oxidizing agent from the encapsulating composition within desired parameters. The resulting encapsulated oxidizing agent has a predictable release profile and releases the oxidizing agent after a period of time when introduced its use environment.
  • the oxidizing agent which is encapsulated with the coating composition is generally a solid oxidizing agent.
  • Exemplary oxidizing agents include, for example, calcium hypochlorite or other hypochlorite salts, 1 ,3-dichloro-5,5-dimethylhydantoin (DCDMH), 1 ,3-dibromo-5,5-dimethylhydantoin (DBDMH), 1 -bromo-3-chloro-5,5- dimethylhydantoin (BCDMH), 1 ,3-dichloro-5-ethyl-5-methylhydantoin (DCEMH), 1 ,3- dibromo-5-ethyl-5-methyl hydantoin (DBEMH), 1 -bromo-3-chloro-5-methyl-5- ethylhydantoin (BCEMH), trichlorochlorotriazine (tri-chlor or TCCA),
  • dichlorochlorotriazine di-chlor and DCCA
  • monochlorotriazine mono-chlor
  • sodium dichloro-s-triazinetrione dichloride persalts, for example, persulfates, per carbonates and the like, including for example sodium persulfate and other other chlorine releasing compounds such as glycouril, sulfosuccinates or the like.
  • oxidizing agents may be in either the anhydrous or hydrated forms. Generally, these oxidizing agents will be in a granular form, having a particle size in the range of about 25 microns to about 2000 microns.
  • the solid oxidizing agents have an outer surface.
  • first coating layer Covering the outer surface of the solid oxidizing agent is a first coating layer.
  • the first coating layer serves to encapsulate the solid oxidizing agent such that the solid oxidizing agent is not exposed once coated with the first coating layer.
  • Suitable first coating layer materials include alkali metal salts and alkaline earth metal salts and hydroxides and other inorganic salts and anhydrides. Of particular interest are sodium chloride and calcium hydroxide as the first layer
  • this first coating layer contains as the predominate component a multivalent metal salt or multivalent metal hydroxide. By the phrase "predominate component" it is intended that the component makes up at least 50 wt% of the first coating layer.
  • Suitable multivalent metals include the alkaline earth metals, e.g. Mg, Ca, and Ba; zinc, copper, aluminum and the like.
  • the term "multivalent” means having a valence greater than or equal to two.
  • Suitable salts include, for example, sulfates, chlorides, phosphates, silicates, and the like.
  • hydroxides of these multivalent metals may also be used.
  • One particular example, for the first coating layer is calcium hydroxide.
  • the first coating layer will have be at least 60 wt% of the multivalent alkali metal salt or metal salt or hydroxide, and typically at least 80 wt%.
  • the weight percentage is of the dried coating on the oxidizing agent.
  • the first coating layer is applied on the solid oxidizing agents in any know manner, including spray dried coating processes. It has been discovered that the multivalent metal salts or hydroxides provide an improved release profile that is easier to control than monovalent metal salts or monovalent metal hydroxides.
  • the multivalent metal salts and/or hydroxides tend to convert the oxidizing agent to an anhydrous form, making the oxidizing agent more stable. This is especially true for the oxidizing agent calcium hypochlorite. Improved stability is important when handling extremely reactive compounds such as calcium
  • the first coating layer is applied to a thickness of the coating in the range of about 0.5 to about 5 microns in thickness. Typically the first coating layer will be in the range of about 1 to about 3 microns. It has been discovered that thicker layers of the first coating layer provides minimal increase in stability or release profile. It has also been discovered that the first coating layer is sufficient to keep the oxidizing agent from reacting with material outside of the first coating layer. That is, when the oxidizing agent is calcium hypochlorite, the first coating layer will protect the calcium hypochlorite from organic materials, such as hydrocarbons, glycerol and the like, which come into contact with the first coating layer.
  • additional coatings may be applied over the first coating layer.
  • the additional coating layers serve to control the release profile of the oxidizing agent from the encapsulating layer.
  • the second or additional layers applied to the first coating layer will be a material that is water soluble. As the second or subsequent layer dissolve in water of the use environment, the water will contact the first layer, dissolving the first coating layer, thereby releasing the oxidizing agent form the encapsulating materials.
  • the second or subsequent layers can be prepared from a wide variety of materials, including organic materials, such as polyvinylalcohol, polyacrylic acid, polyvinylacetate, and other similar water soluble organic materials.
  • the second or any additional coating layers maybe soluble inorganic materials. Soluble inorganic materials suitable for the
  • alkali materials such as sodium bicarbonate, sodium sesquicarbonate, sodium borate, potassium
  • phosphates such as diammonium phosphate, monocalcium phosphate, monohydrate, tricalcium phosphate, calcium pyrophosphate, iron pyrophosphate, magnesium phosphate, monopotassium orthophosphate, potassium pyrophosphate, disodium
  • orthophosphate dihydrate trisodium orthophosphate decahydrate, tetrasodium pyrophosphate, sodium tripolyphosphate, a sodium polyphosphate compound, sodium hexametaphosphate, potassium tripolyphosphate, a potassium
  • polyphosphate compound neutral or soluble salts such as sodium sulfate, sodium chloride, silicates, such as sodium or potassium silicates, tetrasodium or
  • tetrapotassium pyrophosphate pentasodium or pentapotassium tripolyphosphate
  • hydrated or anhydrous borax sodium or potassium sesquicarbonate
  • phytates polyphosphonates and other similar materials.
  • silicates in particular sodium silicate.
  • the release of the oxidizing agent from the encapsulating layer can be controlled by the selection of the second and subsequent encapsulating layer and the thickness of the second and subsequent encapsulating layers.
  • the thicker the second or subsequent encapuslating layers the longer it takes for the oxidizing agent to be released from the encapsulating coating.
  • the second or subsequent encapulslating layer can be up to about 10 microns thick, or thicker depending on the desired release profile.
  • An exemplary thickness for the second and subsequent coating is general in the range of 0.1 -5 microns.
  • the second or subsequent coats of the coating composition are in the range of 0.25-2 microns. It was also unexpectedly discovered that thinner encapsulating layers result in a more stable oxidizer as compared can be achieved by thicker coatings. Stability here is intended to mean heat stability above about 140°F (60°C).
  • the manufacture of the encapsulated oxidizing agent can be carried out by first providing an initial inorganic protective passivation coating of the core material which can be conveniently applied using fluidized coating apparatus.
  • the particulates are introduced into the fluidizing chamber of a fluidized bed.
  • the bed of particles to be coated is then suspended with the fluidizing atmosphere.
  • a nozzle is typically introduced into or nearby the fluidized bed through which liquid droplets of coating material are discharged in a diverging pattern coextensive with the upper surface of the bed.
  • Coating solution is applied to the bed at a temperature required for rapid drying of the coating solution on the core particles. Solvent vapors can be removed from the fluidized bed with a blower.
  • a encapsulated oxidizing agent in the present invention is typically produced by a spray fluid bed coater such as Mini-Glatt and GPCG-1 from Glatt Air Technologies, Inc., and ACT 100N and ACT 300N from Applied Chemical
  • the variables and conditions of coating are specifically controlled to have minimum wetting on the surface of the oxidizing agent particles, and generate suitable mixtures with hydrated salts.
  • a multiple layer coating is accomplished by sequential feeding of deemed coating materials under suitable coating conditions. Coating may be conducted using either a batch or continuous process. Additionally, according to the present invention, a continuous feeding of aqueous coating solution is used to produce a controlled homogenous or heterogeneous single or multilayer coated granular calcium hypochlorite composition.
  • An 100 N fluidized bed spray coater was used to prepare the sample shown in Table 1 .
  • the coated calcium hypochlorite in the following examples shown in Table 1 were produced by an ACT 100N spray fluid bed coater from Applied Chemical Technology, Inc. at inlet air temperature of 50-75° C and product temperatures of 35-55° C.
  • a multiple layer coating was accomplished by sequential feeding of coating materials under the conditions at the same or different inlet and product temperatures.
  • the pump rate of a coating solution was specifically controlled to achieve suitable particle wetting and drying to minimize loss of available chlorine. Typically, the pump rate was set to 10ml/min.
  • these examples were made using a batch process, other processes, such as continuous processes, may also be employed for production of these materials.
  • the encapsulated oxidizing agent of the present invention may be used in any use that requires the use of an oxidizing agent, where delayed release of the oxidizing agent is desirable.
  • exemplary uses include as whitening additive for laundry detergents, as a whitening additive for automatic laundry machines, as a toilet bowl cleaner, as sanitizing additive for an automatic dishwashing machine, as a sanitizing or disinfecting additive for pools and spas and the like.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un agent oxydant solide encapsulé, tel que l'hypochlorite de calcium, qui est encapsulé par une première couche de revêtement qui est de façon prédominante un sel de métal multivalent ou est une composition de revêtement mince d'autres sels. Le sel de métal multivalent recouvre complètement la surface externe de l'agent oxydant solide. Des couches supplémentaires de différents revêtements peuvent être appliquées sur la première couche ou des couches subséquentes des revêtements. Les agents oxydants solides encapsulés résultants sont libérés du revêtement après une période de temps dans l'environnement d'utilisation.
PCT/US2014/054931 2013-09-10 2014-09-10 Agent oxydant encapsulé ayant une libération retardée contrôlée WO2015038597A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361876013P 2013-09-10 2013-09-10
US61/876,013 2013-09-10

Publications (1)

Publication Number Publication Date
WO2015038597A1 true WO2015038597A1 (fr) 2015-03-19

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174411A (en) * 1972-07-31 1979-11-13 Olin Corporation Granular calcium hypochlorite coated with an inorganic salt by spray graining
EP0203239A1 (fr) * 1985-04-30 1986-12-03 Ecolab Inc. Agents de blanchiment d'halogénure enveloppés
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
US4741858A (en) * 1987-03-02 1988-05-03 The Clorox Company Timed-release hypochlorite bleach compositions
US5213705A (en) * 1985-04-30 1993-05-25 Ecolab Inc. Encapsulated halogen bleaches and methods of preparation and use
WO2001052634A2 (fr) * 2000-01-21 2001-07-26 Biobullets Limited Administration de substances a des organismes invertebres
WO2004053040A2 (fr) * 2002-12-05 2004-06-24 Ecolab Inc. Agents de blanchiment encapsules, antimousse et compositions le contenant
WO2007064681A2 (fr) * 2005-12-01 2007-06-07 Arch Chemicals, Inc. Composition d'hypochlorite de calcium enrobe

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4174411A (en) * 1972-07-31 1979-11-13 Olin Corporation Granular calcium hypochlorite coated with an inorganic salt by spray graining
EP0203239A1 (fr) * 1985-04-30 1986-12-03 Ecolab Inc. Agents de blanchiment d'halogénure enveloppés
US5213705A (en) * 1985-04-30 1993-05-25 Ecolab Inc. Encapsulated halogen bleaches and methods of preparation and use
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
US4741858A (en) * 1987-03-02 1988-05-03 The Clorox Company Timed-release hypochlorite bleach compositions
WO2001052634A2 (fr) * 2000-01-21 2001-07-26 Biobullets Limited Administration de substances a des organismes invertebres
WO2004053040A2 (fr) * 2002-12-05 2004-06-24 Ecolab Inc. Agents de blanchiment encapsules, antimousse et compositions le contenant
WO2007064681A2 (fr) * 2005-12-01 2007-06-07 Arch Chemicals, Inc. Composition d'hypochlorite de calcium enrobe

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