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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters

Definitions

• the present invention relates to packaged aqueous liquid bleach compositions which comprise peroxygen bleaches.
• Aqueous liquid bleach compositions comprising peroxygen bleaches are well known in the art. It is well known that such compositions are not fully compatible with all packaging materials. Specifically, such compositions may cause so-called bulging problems when they are packaged in containers made out of deformable materials, typically thermoplastic materials. Indeed, the peroxygen bleach in the composition decomposes with time so as to generate oxygen in the composition. The released oxygen builds up pressure inside the container which eventually deforms, i.e. bulges. The problem is more acute in warm countries where decomposition is favored by heat.
• venting caps which let gasses out from the containers, but not liquids. Such caps prevent the building of pressure inside the containers.
• a variety of such caps have been described in the art, but they all have the drawback that they are expensive to make, either because they require sophisticated construction from several parts, or because they require the use of specific materials.
• a third type of solution is the use of so-called leaking caps, where the gasses are let out of the bottles for instance through the threads of the cap, between the inner wall of the cap and the outer wall of the container onto which the cap is screwed. This has the drawback of letting not only gasses through but also some of the liquid contained in the container.
• DPA dipicolinic acid
• the invention encompasses a closed deformable container containing a liquid aqueous composition comprising a peroxygen bleach and an effective amount of dipicolinic acid.
• the invention encompasses the use of dipicolinic acid, in a liquid aqueous bleach composition having a pH of from 1 to 5 and comprising a peroxygen bleach, to prevent the bulging of the deformable container containing said composition.
• a first essential element of the present invention is the closed deformable container which contains the liquid bleach composition.
• the containers for use herein are bottles, i.e. they comprise a body portion and a neck.
• the bulging problem is particularly a nuisance when using bottles, as the bottle deforms at its base when pressure builds up, and this compromises the stability of the bottle upon standing. It is not unusual to observe that the base is deformed to the point where the container cannot stand on its base at all. One will appreciate that this is a problem not only for the consumers but also for the trade. Bulging also happens in other containers such as bulk containers and is also a problem there, but to a lesser extent.
• preferred containers herein are bottles comprising a body portion comprising a base on which the bottle stands, and a neck portion which comprises means for attaching a closure. Said bottles may of course comprise a variety of other items, typically handles.
• the containers herein are closed containers. By closed, it is meant herein that pressure can be generated inside the container, i.e. the container does not have a free communication with the ambient.
• This definition includes closures which allow a partial communication with the ambient, i.e. so-called venting caps inasmuch as venting caps may not be enough to control bulging. But the bulging problem is particularly acute with closures which are substantially air tight.
• the present invention finds a preferred application when using air tight closures.
• the containers herein are reclosable, and a suitable closure for this purpose is a conventional cap having a screw thread on the inside which corresponds with a screw thread on a portion of the container.
• deformable containers which are closed by a seal
• Such containers are typically designed for a single use since they cannot be closed after they have been opened.
• Such containers which are typically in the form of sachets or pouches, usually do not stand on a base, but bulging is still a problem in this case as it might cause said seal of said pouch to rupture under pressure.
• the container herein must be deformable. Indeed, if it is not deformable under the pressure generated inside it, then the bulging problem does not exist. Accordingly, such containers as glass containers are not included herein because they do not deform under internal pressure, even when they are closed. Containers made of thin metal material like Aluminium sheets can bulge and are therefore included herein. But the most commonly used deformable materials for making containers, especially bottles are thermoplastic materials, and thermoplastic materials are deformable under internal pressure even when fairly thick materials are used. Furthermore, a trend in today's packaging is clearly towards the use of so-called lightweight thermoplastic packages, i.e.
• thermoplastic materials typically between 0.1 mm and 0.2 mm thick for pouches and between 0.5 mm to 2 mm for bottles, preferably 0.5 mm to 2 mm. These thin thermoplastic materials are of course very deformable and thus it becomes highly relevant to prevent bulging in these containers.
• Thermoplastic materials suitable for use herein include virgin and recycled materials and mixtures thereof, vinyl chloride based resins, polymers and copolymers derived from olefins, acrylic polymers and copolymers, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, or mixtures thereof.
• compositions comprising peroxygen bleaches must be protected from UV and visible light in order to prevent decomposition as much as possible. This is typically ensured by using appropriate pigments, so-called masterbatches, in said thermoplastic materials.
• masterbatches in said thermoplastic materials.
• Thermoplastic materials for use herein can be single layer or multilayer materials.
• a second essential element of the present invention is the liquid bleach composition contained in the closed deformable container.
• the composition herein is an aqueous composition which comprises a peroxygen bleach or mixtures thereof, preferably hydrogen peroxide.
• Compositions herein include simple bleaching compositions as well as fully formulated consumer products which typically comprise other ingredients such as surfactants, solvents, chelants, polymers and the like.
• a first essential element in the compositions herein is the peroxygen bleach.
• the bulging problem comes from the reaction of oxygen with metal ions and radicals in the composition, which generates gas. Thus said reaction is likely to happen as soon as there is oxygen in the composition.
• the compositions herein may comprise any peroxygen bleach capable of yielding oxygen in the composition. This includes alkali metal peroxides, organic peroxides such as urea peroxide, preformed peracids such as nonylamide peroxyadipic acid, inorganic persalts such as perborates, percarbonates and the like. All of these eventually yield hydrogen peroxide, thus oxygen in the composition.
• the compositions according to the present invention may comprise from 0.5% to 30% by weight of the total composition, preferably from 1% to 15%, most preferably 3% to 10%, particularly if hydrogen peroxide is used.
• An essential element of the composition in the present invention is the presence of dipicolinic acid. Indeed, we have found that the presence of dipicolinic acid prevents the bulging of the container containing the composition.
• the desirable amount of dipicolinic acid is depending on various factors such as the specific container used and the specific formulation used, but it can be determined by simple trial and error.
• the composition herein should comprise dipicolinic acid in a weight ratio of bleach, particularly hydrogen peroxide, to dipicolinic acid of from 1550:1 to 1.4:1, preferably 1000:1 to 1.4:1 and more preferably 800:1 to 10:1.
• peroxygen stabilizers including butyl hydroxy toluene, etidronic acid, diethylene triamine penta methylene phosphonic acid (DTPA), benzoic acid and ethylene diamine-N,N'-disuccinic acid do not provide the anti bulging benefit, even at higher levels.
• compositions herein be formulated at a pH of from 1 to 6, preferably 2 to 5. Indeed, we speculate that the pH of the composition might affect the DPA's ability to prevent bulging.
• compositions herein may comprise a variety of optional ingredients such as H2O2 stabilizers such as radical scavengers and chelants, surfactants, solvents, polymers, perfumes, dyes and the like.
• H2O2 stabilizers such as radical scavengers and chelants, surfactants, solvents, polymers, perfumes, dyes and the like.
• Suitable method for the determination of DPA present in the compositions according to the present invention is a potentiometric titration with CU(NO3)2 using a cupric electrode (Orion model 94-29®). Indeed, in said method 10 g. of a composition according to the present invention are weighted in a titration beaker. Then about 30 mL of buffer solution (Buffer : 6.4 g Na2B4O7.10H2O + 8.3 g H3BO3 in 1000 mL deionised water) is added. Then a potentiometric titration is carried out, using a cupric electrode, with Cu(NO3)2 0.01 N. However, before starting the titration, a stirage of about 80 seconds in order to equilibrate the electrode in the sample solution takes place. The increments of titrant to add should be maximum 0.01 mL and minimum 0.005 mL.
• % DPA (Volume Cu(NO3)2 * Normality Cu(NO3)2 * 33.4)/ sample weight.
• Compositions 1 to 6 were made as indicated (in weight %) and then used to fill identical containers.
• the containers used were with HDPE with 4% masterbatch.
• the bottles were 1 Lit. Bottles, about 280mm high, about 120mm deep and 65mm wide. The thickness of the walls of the bottles ranged from 0.7mm to 1.6mm.
• Containers were closed with an air tight cap with a screw thread. To ensure air tightness during the test, silicone bands were added on the threads and caps were sealed with a tape.
• the filled and closed containers were then stored at 50°c for the indicated periods. The results are shown at the bottom of the table (B stands for bulged, SB stands for slightly bulged, NB stands for not bulged).

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Closures For Containers (AREA)
• Packages (AREA)
• Detergent Compositions (AREA)

Priority Applications (4)

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• 1994
  • 1994-06-08 EP EP94201633A patent/EP0666307A3/de not_active Ceased
• 1995
  • 1995-01-31 AU AU18361/95A patent/AU1836195A/en not_active Abandoned
  • 1995-01-31 WO PCT/US1995/001279 patent/WO1995021122A1/en active Search and Examination
  • 1995-01-31 JP JP7520700A patent/JPH09508342A/ja active Pending

Patent Citations (2)

Non-Patent Citations (1)

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