A controller includes a body having a handle, and an array of proximity sensors spatially distributed on, in, beneath, or near the outer surface of the handle, responsive to a proximity of a user's fingers to that outer surface. A finger tracker converts the output of the array of proximity sensors to a set of joint angles corresponding to a plurality of the user's fingers. The controller may include a renderer for processing the joint angles to deform a hand mesh that is rendered for display. Values may be calculated to facilitate normalization of the output of the proximity sensor array and thereby generate a set of normalized finger detection data. This data may be processed through curl logic to produce a linear estimate of gross finger curl with respect to the user and thereby generate a set of estimates for a plurality of finger joint angles for the user.

Various hand-held video game controllers have been designed, manufactured, and sold, for a variety of game applications. Some innovations in hand-held controller technology have applicability outside of the video game industry, such as for controllers of industrial machines, defense systems, robotics, etc. Virtual reality (VR) systems are an application of great contemporary interest and rapid technical advancement, both within and outside of the video game industry. Controllers for VR systems are designed to perform several different functions and meet strict (and sometimes competing) constraints, often while optimizing certain desired characteristics such as ease of use and user-defined configurability, for example.
A variety of augmented and/or virtual reality systems and/or environments are known. One current generation of desktop VR experiences is created using head-mounted displays ("HMDs"). Such desktop VR experiences generally try to be fully immersive and disconnect the users' senses from their surroundings.
In the exemplary environment of HMDs typically used in some VR systems, a human user wears a head-mounted virtual reality apparatus that includes displays in close proximity to each of the user's eyes, headphones or other sound-producing devices in or near the user's ears, and one or more hand-held controllers. FIG. 1 is an exemplary diagram of a human user (10) wearing a head-mounted VR display apparatus (22) comprising optical receivers and sensors (23a, 23b, 23c, etc.) that may be used for tracking the position and orientation of the VR display apparatus. Without limitation, HMD's may be tethered to a stationary computer (such as a personal computer ("PC"), laptop, or game console), or alternatively may be self-contained (i.e., with some or all sensory inputs, controllers/computers, and outputs all housed in a single head-mounted device).
Various techniques are known for transposing a physical control device held by the user (also referred to as a controller) into a virtual reality environment in a realistic or augmented form, thus simulating the actual control device held by the user or a variation thereof that is tailored to the virtual environment and/or provides context-specific information. For example, FIG. 2 depicts an exemplary display in a virtual reality environment (50), in which a virtual image of a real game control device (52) is in view of a human user (such as user 10 shown in FIG. 1) who is holding the control device in the real physical environment and wearing a head-mounted VR display apparatus (such as apparatus 22 shown in FIG. 1). For reference, the display in the exemplary virtual environment (50) depicted in FIG. 2 also includes virtual representations of a table (54) and a window (56). A controller program provides the user with a virtual representation of the user's physical control device (52) that can either be realistic or augmented to reflect the virtual context and/or function of the control device and its interactive elements. As the user moves the actual control device in the real physical environment, these movements may be tracked using various techniques known in the art and further described herein to enable corresponding movement of the virtual representation of the control device (52) within the virtual reality environment.
However, the ability to detect and display specific details regarding the position of the user (or parts of the user), the HMD, one or more of the hand-held control devices that may be in use, or any other aspect of the real physical environment depends on the specific configuration of any sensors and tracking systems that are deployed in the HMD VR system. For example, as is well known to skilled artisans, accurate representation of the position and orientation of the HMD and of the associated controllers requires use of appropriate object tracking technology. Similarly, accurate detection and/or representation of where the user may be directing his or her gaze may require use of appropriate eye-tracking technology.
To further improve a user's experiences with systems such as VR HMDs, it would be advantageous to provide better solutions for tracking and displaying the position of one or more of a user's fingers as the user moves his or her fingers relative to a part (such as the handle portion) of a control device that the user holds during a VR session.
Hence, there is a need in the art for improved controller designs and techniques that may improve systems such as VR HMDs and/or better facilitate user operation by providing new finger tracking and/or gesture detection solutions.

This patent is subject to a terminal disclaimer.

Electronic controller with finger motion sensing


An image processing system in which a process for implementing part of the display management function is provided separately from the window system or the operating system. In consequence, changes in the system configuration can be coped with only by conducting addition on a user program or the process which implements part of the display management function without modifying or altering the window system or the operating system. This eliminates modification or alteration of the window system or the operating program and increases the portability of the program.

1. Field of the Invention
The present invention relates to an image processing system, and more particularly, to a window system suitable for processing images which are displayed on a plurality of display devices.
2. Related Background Art
In a conventional image processing system, an image-only display is connected to an engineering work station (abbreviated to EWS), and images are displayed on the image-only display. In that case, a bit-map display may also be used to display images. Generally, in the case of display of images on a display, such as an on the image-only display, an image-only display display processing routine is called to perform display. Thus, when images are to be output to the EWS, a display processing routine offered by the EWS is called. In the case of the EWS, a multi-window system may be activated, and images may also be displayed in the windows. The multi-window system may be incorporated in the operating system (abbreviated to OS) of the EWS or be provided separately from the operating system as an individual process.
On such a system, display management may be performed, e.g., the display destination may be changed over from, for example, the image-only display to the window. Alternatively, the image may be temporarily saved on the display of the EWS in the form of an icon (a symbol). The associated functions may be incorporated in the process which implements the window system or in the operating system.
However, in that system, when changes occur in the system configuration, including the image processing hardware, the number of planes on the bit-map display of the EWS, and the number of displays connected to the system, the program which performs display and management of images, such as the process which implements the window system or the operating system, must be modified or altered. However, modification or alteration of the program itself is a troublesome task, and increases production cost. At the same, the portability and modularity of the program are degraded.


The invention is a system of arrow vanes of novel geometry. The leading edge of each vane is parallel to the long axis of the arrow shaft, and the trailing edge of each vane is deflected out of the plane of the vane like an airfoil causing rotation during flight. All vanes of the invention are identical with all deflected portions facing the same direction when the arrow is viewed down its long axis. The invention also includes one or more vents in the vane surface. Careful placement of these vents decreases aerodynamic drag upon initial release from a bow and also once rotational speed is achieved.

1. Field of the Invention
The present invention relates to the field of archery. Specifically, the invention relates to the vanes or fletching found on arrow devices.
2. Description of the Prior Art
Bowhunting and archery rely on arrows to have two key properties. First, arrows must achieve penetration of the intended target regardless of whether that intended target is a static bulls-eye or a hunted animal. Second, arrows must fly straight and true. Even the most skilled of archers, with the most trained eyes, can not compensate for an arrow that can not find its intended mark. These two great needs are somewhat at odds with one another. Historical solutions have sought to balance these two needs in order to minimize the detrimental effects of each while maximizing the overall result.
The problem of target penetration has been addressed in several ways. Target penetration can be directly correlated to the likelihood of hunting success: an arrow that can not adequately penetrate an intended animal is of little use to a hunter. The overall mass of the arrow could be increased, but more massive arrows are clumsy and must be fired in a high arc to reach the intended target. Simple xe2x80x9cfield pointxe2x80x9d arrow tips can provide adequate penetration for targets in competition, but they are not very effective for killing hunted animals. Prior art broadhead arrows were invented to increase effective hunting penetration and success potential. Typically two to four flat, triangular blades are arranged around the forward pointed tip. As the tip enters the intended target, the blades slice a region much greater than the diameter of the arrow shaft. Unfortunately, these broad, flat blades have a pronounced aerodynamic effect that can radically affect the overall stability of the arrow in flight and significantly reduce the precision of flight. Since the majority of hunting tips are broadhead in design, the combined effect of broadhead and fins at opposite ends of an arrow may not promote a stable flight.
Simple fletching, or other guidance fins, were added to the aft end of prior art arrows. Typically, two to four fins are applied parallel to the long axis of the arrow surrounding the aft end. As the arrow sails through the air, these fins are intended to straighten the overall flight path by effectively pushing the tip of the arrow in the right direction. Prior art, commercially available arrows, also teach applying the fins in a slightly helical or off-main axis manner to the arrow shaft. Such an arrow spins, once released, in order to promote a truer flight. However, these same fins typically account for sixty percent of the overall aerodynamic drag experienced by the arrow in flight. Fins of reduced size have less drag but also provide less overall stability. Minimizing drag is important to increase overall range and speed at impact. Virtually all prior art arrow vanes are constructed of materials which flex or bend when the arrow is first released due to aerodynamic forces. As a result they fold almost flat when the arrow is released and do not apply sufficient torque to the arrow to bring it to a speed of rotation adequate to ensure stability until significant deviation from the initial course has occurred. The only prior art vanes which are constructed of rigid plastic either have very high aerodynamic drag due to sharp projecting angles or are incompatible with a standard arrow rest.
The present invention is a system of arrow vanes that provide excellent main shaft rotation without producing a large amount of aerodynamic drag. A plurality of modest vanes are attached around the aft end of any conventional arrow shaft or integral to the aft end of any conventional arrow shaft. The invention is compatible with all contemporary arrow shafts.
A key feature of the current invention is that each vane constitutes an airfoil, with the airfoils together acting as an axial flow turbine, to maximize the twisting force or torque applied to the arrow while simultaneously minimizing aerodynamic drag at both low and high rates of rotation. To achieve this, the airfoil is a curved surface, like the wing of an aircraft, and also varies in pitch from zero at the base to a maximum pitch at the tip, which may be as great as 30 degrees. When the arrow is rotating rapidly, the portion of the vane near the tip is moving through the air in a spiral path. The gradual variation in pitch along the length of the vane ensures that the portion of the vane near the tip is aligned along the path it follows through the air, minimizing drag. This same principle of changing pitch with radial distance is well established in the design of aircraft propellers and turbines, but has never been applied to the design of arrow vanes.
In the present invention, the geometry of each vane constitutes an airfoil wherein the leading edge of each vane is parallel to the long axis of the arrow shaft, and the trailing edge of each vane is deflected out of the plane of the vane like an airfoil. All vanes of the present invention are identical with all deflected portions facing the same direction when the arrow is viewed down its long axis. In flight, the arrow rotates as a result of airflow over the deflected portion of the vanes much as the control surface on an aircraft wing changes the direction of the aircraft if said control surface is deflected out of the major plane of the aircraft wing.
Another key feature of the present invention is one or more vents in the vane surface. Careful placement of these vents decreases aerodynamic drag upon initial release from a bow and also once rotational speed is achieved.


A continuously variable transmission (CVT) having a main shaft configured to support and position various components of the CVT. Shift cam discs cooperate with ball-leg assemblies to shift the transmission ration of the CVT. Load cam discs, a torsion disc, rolling elements, and a hub cap shell are configured to generate axial force, transmit torque, and manage reaction forces. In one embodiment, a splined input shaft and a torsion disc having a splined bore cooperate to input torque into the variator of the CVT. Among other things, various ball axles, axle-ball combinations, and reaction force grounding configurations are disclosed. In one embodiment, a CVT having axial force generation means at both the input and output elements is disclosed.

1. Field of the Invention
The field of the invention relates generally to transmissions, and more particularly to continuously variable transmissions (CVTs).
2. Description of the Related Art
There are well-known ways to achieve continuously variable ratios of input speed to output speed. The mechanism for adjusting an input speed from an output speed in a CVT is known as a variator. In a belt-type CVT, the variator consists of two adjustable pulleys having a belt between them. The variator in a single cavity toroidal-type CVT has two partially toroidal transmission discs rotating about a shaft and two or more disc-shaped power rollers rotating on respective axes that are perpendicular to the shaft and clamped between the input and output transmission discs.
Embodiments of the invention disclosed here are of the spherical-type variator utilizing spherical speed adjusters (also known as power adjusters, balls, sphere gears or rollers) that each has a tiltable axis of rotation; the adjusters are distributed in a plane about a longitudinal axis of a CVT. The rollers are contacted on one side by an input disc and on the other side by an output disc, one or both of which apply a clamping contact force to the rollers for transmission of torque. The input disc applies input torque at an input rotational speed to the rollers. As the rollers rotate about their own axes, the rollers transmit the torque to the output disc. The input speed to output speed ratio is a function of the radii of the contact points of the input and output discs to the axes of the rollers. Tilting the axes of the rollers with respect to the axis of the variator adjusts the speed ratio.


A process for stabilising particulate alkali metal percarbonate involves coating it with an aqueous solution, preferably concentrated, of a non-reducing oligomeric saccharide, preferably sucrose and especially together with an inorganic salt co-coating agent. The preferred co-coating agents are alkali metal silicate, sulphate, carbonate and carbonate chloride. Coated percarbonate is provided having an excellent combination of solubility, and stability, even with low amounts of coating agent.

The present invention relates to a process for stabilising particulate alkali metal percarbonate, and particularly to a coating process therefor, to the particulate percarbonate having improved stability so produced and to washing or bleaching compositions containing the same.
It is well known that particulate alkali metal percarbonates, including sodium percarbonate in particular, can be used as bleach additives for addition to detergent compositions, and as bleaching compounds in detergent powder mixtures, eg for domestic clothes washing or in dishwashing compositions. In comparison with alkali metal perborate tetrahydrate, they have the advantage of dissolving more rapidly at temperatures in the range of 20xc2x0 C. to 40xc2x0 C., which is becoming increasingly beneficial in view of the trend towards lower clothes washing temperatures and the use of a bleach activator in conjunction with the bleach. Another advantage of percarbonates is that they are environmentally friendly. However, percarbonates have a known disadvantage of decomposing more quickly than sodium perborate tetrahydrate during storage in the powdered state, particularly if stored in a damp atmosphere and in washing or detergent compositions. Moreover, other constituents of washing compositions such a alkaline builders are known to accelerate the rate of decomposition of percarbonates.
In order to improve the stability of percarbonates, and particularly sodium percarbonate, it has been proposed to treat the surface or the surface layer of the percarbonate particles with a wide range of materials, and in particular to coat or encapsulate the percarbonate with those materials. A wide range of organic and/or polymer compounds such as paraffins, carboxylic acids, polyols, vinyl resins etc. and inorganic compounds such as silicates, borates, perborates, boric acids, carbonates, chlorides, sulphates and phosphates have been proposed as coating materials. There remains, however, a continuing need to locate alternative or improved means for improving the stability of percarbonates.
In WO 95/18065, Solvay Interox has disclosed the use of complexes of boric acid with polyols or hydroxycarboxylic acids as coating agents for percarbonates, including, without any particular emphasis, complexes of boric acid with saccharides. Research has shown that coating agents incorporating boric acid or borates are amongst the most effective coating agents for stabilising percarbonate, including their complexes with the polyol/hydroxycarboxylic acids, but some potential customers for percarbonates dislike the presence of boron possibly because they fear that its use in bleaching or washing compositions may be prohibited or curtailed. Accordingly, it remains desirable for producers of percarbonate to continue to try to develop boron-free coating materials.
In the course of devising the instant invention, a number of the organic materials were tested which had been contemplated in WO 95/180650 in complexes with the oxyboron compound. Amongst those materials, saccharides were tested and it was found that there was a substantial difference between them in their performance at stabilising the percarbonate, and particularly when the percarbonate is incorporated in detergent or washing compositions. In particular, it was found that lactose, alternatively called milk-sugar, provided relatively poor stability when employed in a low proportion, even though it was alleged by Sunstar KK et al in JP 60116625 that a peroxide (5% potassium persulphate and 26% sodium percarbonate) coated with 15-25% milk sugar showed good stability in an artificial teeth cleaning composition.
The present invention provides a process for stabilising a particulate alkali metal percarbonate by coating it with an effective amount of a coating material characterised in that the coating material comprises not more than 5% by weight, based on the coated material of a non-reducing oligomeric saccharide.
Herein by the term effective amount is meant an amount such that the rate of decomposition of percarbonate is reduced in comparison with the corresponding uncoated percarbonate, for example when stored in an atmosphere at 80% relative humidity and 32xc2x0 C. in the presence of its own weight of zeolite 4A as described hereinafter.
Herein, during the coating process, the coating material is brought into contact with the particulate percarbonate, and especially suitably in the form of an aqueous solution.
Without being bound by any theory, it is believed that the effectiveness of coatings obtained in the present process may be assisted by the ability of solutions of the selected non-reducing oligomeric saccharides to spread easily across the surface of the percarbonate and thereby create a barrier or layer from even small amounts of coating agent that prevents or reduces interaction between the percarbonate core and the environment, be it water vapor in the local atmosphere and/or other particulate materials in for example detergent compositions in which percarbonate is incorporated as a bleach. However, easy spreadability of a solution of the coating a gent in practice is believed to contribute only a part of the overall explanation as to how or why the selected coatings are so effective, because other sugars such as lactose are likewise capable of spreading across the surface, but do not exhibit the same performance.
The non-reducing oligomeric saccharide is preferably a disaccharide, and particularly sucrose. It will be recognized that as employed herein, a reference to sucrose includes the molecule itself and any polymeric derivatives that are derivable during processes for applying a coating to percarbonate. For example, during some processes for applying a coating and in most processes for drying a coated percarbonate, it is normal practice to contact the percarbonate particles with a hot gas, which may encourage polymerization. For the avoidance of doubt, the derivatives of sucrose, if any, that arise during such coating or drying processes are encompassed within the instant invention.
It will be recognized that the term oligomeric saccharide excludes starch and like extremely high molecular weight materials.
The sucrose or other non-reducing oligomeric saccharide need not constitute all the coating agent. Indeed, it is preferable for the coating agent to further comprise at least one co-coating agent which can be a salt of a carboxylic or organophosphonic acid, but which advantageously is an inorganic salt. The salt may be employed as such or in the instance of for example carboxylic acids can be incorporated in the solution employed for coating as the corresponding acid which is neutralized by contact with the percarbonate during the coating process. By so employing a co-agent, it is possible either to increase the total coating level without increasing the amount of sucrose or other non-reducing oligomeric saccharide that is coated onto the percarbonate or to achieve the same total weight of coating but with a smaller proportion of sucrose or other non-reducing oligomeric saccharide. In some preferred embodiments of the present invention, the non-reducing oligomeric saccharide provides a minor fraction of the total weight of coating agent.
It will also be understood that although oligomeric saccharides can be employed in a small amount as a coating agent on an oxidizing agent such as sodium percarbonate safely, ie as demonstrated by low heat emission in a standard test, the use of significantly larger amounts result in much greater heat emission which demonstrates that the product is much less safe than uncoated material. Accordingly, it is of practical significance that the proportion of sucrose or other non-reducing oligomeric saccharide employed in the present invention be severely restricted. The potential oxidative interaction between sodium percarbonate and a oligomeric saccharide accordingly represents a major difference between sodium percarbonate and other detergent ingredients like zeolites as such or bearing absorbed additives which do not undergo such oxidative interactions
It has been observed that in at least some methods of applying a coating containing the non-reducing oligomeric saccharide, for example in solution onto a bed of percarbonate particles, there is a growing tendency for the resultant product to contain agglomerates as the weight proportion of the non-reducing oligomeric saccharide is increased above about 2%. This tendency can be ameliorated by employing a co-coating agent as described herein, and in any event, the agglomerates can be disintegrated into constituent particles by gentle pressure, ie pressure that is significantly below that at which compaction would be carried out. It is a process advantage to avoid use of additional processing steps, so that it is distinctly desirable to employ a co-coating agent and indeed. desirable to employ a mixture of the coating agents instead of separate additions where more than one agent is used, though the latter method remains viable, particularly if the additions occur simultaneously onto an agitated bed of particles.
The co-coating agent is often selected from inorganic salts, preferably alkali metal or alkaline earth metal salts and more preferably an alkali or alkaline earth metal carbonate, sequicarbonate or silicate or salt of a mineral acid, such as chloride, sulphate or phosphate. Within the term silicates are encompassed materials which suitable obey the formula M2O.nSiO2 in which M represents an alkali metal preferably sodium or ammonium, and n is selected in the range of from 0.5 to 4. Within the term phosphate, there are encompassed ortho, pyro and metaphosphates or mixtures thereof. Preferred selections of inorganic salts for employment in combination with the non-reducing oligomeric saccharide include carbonate, carbonate/chloride, carbonate/sulphate carbonate/chloride/sulphate, sulphate, sulphate chloride and either silicate or any of the foregoing combinations together with silicate. The weight ratio of carbonate to respectively chloride or sulphate and sulphate to chloride is often chosen in the range of from 10:1 to 1:10 in such combinations. When silicate is present, it often comprises from 2 to 15% of the inorganic salts.
In many preferred embodiments of the present invention, the coating applied to the percarbonate comprises from 5 to 80 parts by of a non-reducing oligomeric saccharide, particularly sucrose together with respectively 95 to 20 parts by weight in total of one or more inorganic salts selected from an alkali metal carbonate, sequicarbonate, silicate-chloride, sulphate or phosphate, and especially from 10 to 60 parts by weight of the non-reducing oligomeric saccharide together with 90 to 40 parts by weight of said selected inorganic salt(s). More desirably, the inorganic-salts or combinations thereof are selected from the preferred selections listed above.
Especially desirable combinations of coating agents according to the present invention comprise from 15 to 50 parts by weight of sucrose in conjunction with 85 to 50 parts by weight of sulphate or silicate.
Instead of all or part of the inorganic salts, it is possible to employ a salt and especially an alkali metal salt such as sodium or magnesium of a carboxylic acid or hydroxycarboxylic acid. Suitable salts include tartrate, citrate, succinate, glutarate adipate and ascorbate, and preferably the sodium, potassium or magnesium salts thereof Mixtures of such salts can be used, as for example mixtures of succinate, glutarate and adipate.
It is highly desirable to select as co-coating agents those which are readily water soluble in the range of ambient temperature to mildly elevated, such as from about 10xc2x0 C. to 40xc2x0 C. or 60xc2x0 C., which encompasses temperatures usually encountered in cold steeping and low temperature machine washing or hand-washing laundry processes or in cleansing of hard surfaces. Such co-coating agents include alkali metal sulphates, chlorides, phosphates and low molecular weight carboxylates like tartrate, adipate or succinate. The choice of a soluble coagent with sucrose or other oligomeric saccharide enables rapid dissolution of the percarbonate in use.
The coating agent or combination of coating agents of the present invention is advantageously employed in the form of an aqueous solution. In practice, the concentration of the coating agent, ie the total of the non-reducing oligomeric saccharide and any co-coating agent, in the aqueous coating solution is at least half of, and preferably as close as is convenient to, its saturation concentration of the solution at the application temperature. In this way, only a comparatively small and preferably at or near the smallest practicable quantity of water needs to be evaporated subsequently to produce dry percarbonate particles, thereby requiring a lesser or least heat input during the drying stage, but retaining the advantage of applying the coating agent in a solution which can spread across the surface of the percarbonate. The concentration of coating agent in the aqueous coating solution is generally at least 15% by weight, preferably at least 20% by weight. Concentrations above or equal to approximately 25% by weight are particularly advantageous and in many instances, the coating agents are sufficiently soluble that solutions containing between 30 and 35% by weight solute in 70 to 65% by weight water can be employed at a solution temperature in the region of 30 to 50xc2x0 C. In some combinations, such as with soluble silicates it is possible even to employ coating solutions containing from 35 to 43% by weight coating agent and the balance water (65 to 57%) at such temperatures. It will be recognized that the coating agent solutions contemplated herein remain free flowing at application temperatures, particularly when a mixture of non-reducing oligomeric saccharide and co-coating agent is employed, thereby assisting the percarbonate particles to absorb at least a fraction of the solution during the process of applying the coating agent and to assist in the rate of spreading of the solution across their surfaces. Such freeflowing capability of the solution, the excellent water solubility of the coating agent or agents and also using a mixture of agents each reduce a risk that oligomeric saccharide dust could be formed inadvertently in contact or in close proximity to a ready source of oxygen.
The dissolution of the coating agent or its constituents can take place conveniently at a temperature of from 15 to 95xc2x0 C., and preferably from 20 to 70xc2x0 C.
It will be recognized that it is not necessary for all the coating agent constituents to be dissolved in a single solution, and that each constituent or a sub-combination can be introduced separately, though such separate employment would tend to increase the amount of solution needed per weight unit of coating agent.
It will also be recognized that a slurry of the coating agents can be employed instead of a solution, for example a suspension of particulate inorganic salt in a solution of the sucrose or other non-reducing oligomeric saccharide. This would enable a relatively large weight of coating to be applied in a single pass, but in practice usually requires small particulates of mean size below 100 microns to be processed.
The total quantity of coating agent used, including both non-reducing oligomeric saccharide, particularly sucrose, and any co-coating agents, usually represents 0.5 to 20% w/w of the coated percabonate Preferably, the total quantity is selected in the range of from 1 to 15% w/w and in many instances from 2 to 10% of the coated percarbonate. In many practical embodiments, the total weight of coating agent is selected in the range of from 2 to 5%. The weight of sucrose or other non-reducing oligomeric saccharide is not more than 5%, is usually selected within the range of from 0.2 to 3%, in many instances from 0.5 to 2.5% and in a number of favoured instances in the range of from 1% to 2% with the balance of total coating agents weight being supplied by appropriate amounts of co-coating agent or agents, and in particular inorganic agents such as those indicated herein. The co-coating agent or mixture of them, it will be seen, often provides a weight of from 0.5 to 6% of coating based on the weight of the coated material, and in many instances from 1 to 3%.
As a general indication, when a coating agent is applied by the same method, the extent to which percarbonate decomposition is ameliorated increases as the thickness of the coat increases, though non-linearly. The selected weight of coating takes into account the manner of coating, the length of the period for which the resultant composition should remain stable, the environment in which the percarbonate will be used, such as the temperature and humidity of storage conditions and the proportion of relatively aggressive washing composition constituents like zeolites, and the extent to which purchasers of the product will tolerate a reduction in the available oxygen (Avox) content of the percarbonate.
The alkali metal percarbonate is preferably sodium percarbonate. In many of the coated percarbonate products produced according to the present invention, the bulk density of the percarbonate so coated is selected in the range of 0.8 to 1.2 kg/l. The rate of dissolution of percarbonate that has been so coated is often acceptably rapid, when determined according to a method adapted from international standard ISO 3123-1976. The time corresponding to a 90% dissolution of the sample of percarbonate coated according to the invention does generally not exceed 2.5 minutes. The 90% dissolution time is the time taken for conductivity to achieve 90% of its final value after addition of coated sodium percarbonate to water at 15xc2x0 C. and 2 g/l concentration. The method used is adapted from ISO 3123-1976 for industrial perborates, the only differences being the stirrer height that is 1 mm from the beaker bottom and a 2 liter beaker (internal height 183 mm, internal diameter 127 mm).
The particulate percarbonate that is suitable for coating in any process according to the present invention can have been prepared in any process known as such for making an alkali metal percarbonate, e.g. by the direct method, by fluid bed processes, or the so called wet processes in which percarbonate is crystallized from a saturated aqueous solutions, often by cooling and/or by optional addition of an alkali metal salt.
Advantageously, in a number of embodiments it is desirable to employ as feedstock a percarbonate that does not contain a significant proportion, ie contains not more than 1% w/w of a halide such as chloride. By selecting such a feedstock, obtainable from a suitably controlled and operated fluidized bed or xe2x80x9cwet bedxe2x80x9d process, it is possible to obtain a particularly beneficial combination of properties, part from the selected coating agent and part from the feedstock so as to achieve the best result overall.
The percarbonate core particles which are coated by a process according to the present invention can incorporate various additives in a wide range of proportions and in accordance with known teachings and/or practice. Such additives include, amongst others persalt stabilizers, crystal habit modifiers and salting out agents.
Persalt stabilizers can be selected from one or more of alkali metal and alkaline earth metal silicates, alkali metal and alkaline earth phosphates, magnesium compounds such as magnesium sulphate, chloride or oxide, organic complexing carboxylic acids and their salts, such as ethylene diamine tetraacetic acid and/or salt, or diethylenetriaminepentaacetic acid and/or salt and/or organic polyphosphonate complexing agents such as hydroxyethylidenediphosphonate, and alkyl eneaminopolymethylenephosphonates, including ethylenediaminetetramethylene phosphonic acid and/or salt, diethylenetriaminepentamethylenephosphonic acid and/or salt, cyclohexane-1,2-diaminetetramethylenephosphonic acid and/or salt.
In some highly desirable embodiments, the process of the present invention is employed to coat sodium percarbonate which contains a small amount of up to about 0.5% w/w silicate distributed within its particles and optionally a further small amount of up to about 0.5% of a silicate or silicate derivative on the surface of its particles, as a result of the timing and distribution of the addition of silicate in two stages during the crystallization and recovery of the particulate percarbonate, for example product that has been produced by a manufacturing/stabilising process described either in GB-A-1 553 505, published in the name of Interox Chemicals Limited or in GB-A-1 578 062, published in the name of Peroxid-Chemie GmbH
Crystal habit modifiers act on the morphology of the percarbonate crystals and include organic polymeric compounds like polyacrylates and inorganic species such as polyphosphates eg sodium hexametaphosphate.
It will be understood that some agents can simultaneously provide a number of different properties, such as stabilization and crystal habit modification.
Salting out agents have conventionally been used in commercial processes that have been employed in the last 60 years for the crystallization of the percarbonate from solution, and typically are highly water-soluble alkali metal salts, such as sodium chloride, sodium sulphate, or sodium hexametaphosphate. Alternatively, the percarbonate can be produced in a crystallisation process which does not employ a noncarbonate salting out agent, but takes advantage of the relative insolubility of sodium percarbonate compared with sodium carbonate in alkaline conditions and at temperatures in the region of about 10 to 25xc2x0 C.
In some embodiments, the nature of a co-coating agent for percarbonate is selected to match or complement the salting out agent if any, that is employed during its manufacture in a crystallisation process. Thus, if the sodium percarbonate is made with a chloride salting-out agent, it is often convenient to employ a coating which contains sucrose plus chloride or chloride/carbonate. On the other hand, if a chloride-free crystallisation process is used, it is convenient to employ a coating which itself does not contain chloride or more than a very minor fraction of chloride providing no more than about 0.3% chloride on the percarbonate.
The mean diameter of the percarbonate core particles that are coated by a process according to the present invention is at the discretion of the user. The mean diameter is normally at least 100 xcexcm and often not greater than 2000 xcexcm, and in many instances, the mean particle size (MPS) falls in the range of 250 to 1000 xcexcm. However, it is particularly desirable to employ percarbonate having an MPS in the region of from about 500 to 850 xcexcm. In a number of advantageous embodiments of the present invention there is provided coated percarboate having an MPS of at least 600 xcexcm and preferably from about 700 to 850 xcexcm.
The spread of percarbonate particles is at the discretion of the percarbonate producer, but as a practical matter, and as has been realized for many years, it is advantageous for incorporation in particulate detergent compositions for the percarbonate to avoid very fine particles, such as particles of below about 100 or 150 xcexcm, because such particles are inherently more susceptible to environment-induced decompositionxe2x80x94they present a much higher surface area to volume ratio than larger particles and they therefore find it easier and quicker to absorb moisture from the surrounding air. For many particulate detergent compositions, it is also desirable to avoid or minimize particles larger than about 1500 xcexcm, to reduce potential problems of persalt/detergent particle segregation. Thus, in many practical embodiments of the present invention, all or substantially all the percarbonate to be coated can pass through a sieve of 1500 xcexcm and be retained on a sieve of 150 xcexcm, and in at least some preferred. embodiments, at least 80% w/w of the percarbonate is retained on a sieve of 350 xcexcm and passes through a sieve of 1200 xcexcm, desirably having an MPS of at least 600 xcexcm and most desirably from 700 to 850 xcexcm. In the context of its definition in EP 451893, the percarbonate products having an MPS of over 600 xcexcm and at least 80% by weight between 350 and 1200 xcexcm have a morphology index of below 0.03, and when coated in accordance with the instant invention, yet still demonstrate an excellent rate of solubility, excellent in wash performance and excellent in pack stability.
The process according to the present invention by which percarbonate particles are coated with the coating agent described above can comprise any method known in itself for contacting persalts with coating agent. A preferred means for bringing the coating agent into contact with the percarbonate comprises spraying an aqueous solution of the coating agent onto the percarbonate particles. It is particularly desirable for the percarbonate particles to be kept in motion. Thus, a coating process of the present invention can desirably be carried out in a range of apparatuses that can agitate particles, of which practical examples include a fluid bed, a rotating plate, and a rotary mixer into each of which it is convenient to spray the coating agent solution. During the course of the contact, the persalt tends to adsorb, and to some extent absorb the coating agent solution and with simultaneous or subsequent evaporation of the solvent from the coating agent solution, a coating is deposited around the percarbonate core.
It will be recognized that the invention coating process may be conducted in a single pass through the coating apparatus or in a plurality of passes, at the discretion of the user. A plurality of passes is particularly beneficial for application of a heavy coating in that it reduces the amount of solvent that need be removed in each pass and thus reduces or removes the risk of over-wetting the percarbonate before it is dried. A continuous or batch method can be used.
Contact of the coating agent solution with the percarbonate can be carried out at the same time and in the same vessel as evaporation of solvent from the solution and formation of the coating layer. The two steps can alternatively be carried out separately in different apparatus, which may in some cases be of the same type, eg both in fluidized beds or be of different types, such as the mixing step in a rotary mixer and the evaporation step in a fluidized bed.
An apparatus such as a fluid bed is particularly suitable for carrying out simultaneous spraying and evaporation. In such an operation, the temperature of the fluid bed is usually maintained in the range of 30 to 95xc2x0 C. and preferably 60 to 80xc2x0 C.
One particularly advantageous process variation comprises contacting a charge of the percarbonate particles with a solution of the invention coating agent in a separate mixer, particularly a rotary mixer, and drying the wetted percarbonate subsequently in a fluid bed. The solution can be introduced into the mixer by spraying or even via a coarse spray such as one or more nozzles. In this separate mixer variation, the temperature in the mixer is often selected in the range of 10 to 60xc2x0 C. and preferably 20 to 50xc2x0 C. The advantage of employing a solution containing sucrose is that it is able to spread readily across the percarbonate particle surfaces within the mixer. Drying in the fluid bed is then often carried out at a temperature of 50 to 90xc2x0 C. and preferably of from 60 to 70xc2x0 C.
The fluid bed employed herein either for a combined coating/drying process or simply in the drying stage can be operated in accordance with known procedures for coating/drying or simply drying persalts, as the case may be. Thus, any non-reactive gas can be used as the fluidizing gas, including air in particular. The gas can be pre-dehumidified, if desired, and pre-heated to maintain the temperature of the fluid bed at the desired value. It is also possible to use direct heating means for the fluidized bed, such as a tube bundle placed within the fluid bed or a heated jacket around the bed. The upward airflow of fluidizing gas is regulated to maintain the percarbonate particles in an agitated state, ie not settling, but is not so great as to blow the particles, other than fines, out of the fluidizing vessel.
The aqueous coating solution and the percarbonate particles are generally brought into contact at a temperature within about 30xc2x0 C. of each other and preferably within about 5xc2x0 C. of each other.
The proportions of coating agent solution and percarbonate are chosen so as to leave, after drying, the desired weight of coating agent around the percarbonate core. In practice, it is desirable to limit the addition of solution to percarbonate in a fluid bed or mixer to a maximum water content of about 15% w/w so as to minimize or eliminate wetting out problems, more preferably to an amount selected in the range of about 3 to 12% w/w water and often from, about 6 to 12% w/w water. It is normally desirable also to continue drying until the coated percarbonate has a moisture content of below about 1% w/w; such as in the region of 0.1 to 0.7% w/w. The duration of the drying stage is usually determined by such practical considerations as, amongst others, the amount of coating agent solution being applied per unit weight of percarbonate, the residual content of moisture that will be tolerated; the temperature and moisture content of the influent fluidizing gas, whether additional heating is employed for the bed and the rate at which the gas flows through the bed. It will accordingly vary from apparatus to apparatus and be capable of control by a skilled person in the art of coating persalts with the aid of preliminary ranging trials.
It will naturally be recognized that the final form of a coating agent on percarbonate may change as a result of subsequent reaction or processing. Thus, for example, contact of a solution of an acidic coating agent on the surface or in the surface layer of percarbonate of an alkali, may result in the interaction of the acid with the alkali, and the drying stage can release water of hydration from some or all hydrated salts that might be expected to be present at ambient temperature, provided that the drying temperature exceeds the transition temperature for such salts.
It will be seen that the present invention also provides coated alkali metal and especially sodium percarbonate having advantageous properties. In some embodiments, by suitable selection of the coating agent and nature of the core percarbonate, the invention provides coated sodium percarbonate having 90% solubility in the solubility test hereinafter described within 1.7 minutes and an Avox retention of at least 64% and preferably at least 70% after 6 weeks storage in the stability test hereinafter described (set A). Such advantageous coated percarbonate is obtainable by coating percarbonate with a non-reducing oligomeric saccharide and optionally with a co-coating agent.
In preferred embodiments, the above identified combination of coating properties, namely rapid solubility and excellent storage stability is achieved with a coating that represents 2 to 5% by weight of the coated product. This is especially advantageous, in that the benefit of excellent stability is achieved with the application of only a small weight of coating agent. This is not only a cost advantage when compared with employing a larger amount of coating agent, but it also minimizes the inevitable reduction in Avox content of the coated percarbonate compared with the uncoated, feedstock percarbonate. By doing so, it is possible to achieve in a number of preferred embodiments the benefits of high stability and rapid solubility whilst retaining an Avox of above 12.5% w/w, particularly above 13.5% and especially above 14%, depending naturally upon the Avox of the feedstock uncoated percarbonate.
Furthermore, in at least some of the particularly useful embodiments, the coated percarbonate having the desirable combination of solubility and stability properties has a mean particle size of from 600 to 850 xcexcm and preferably at least 700 xcexcm. Such a mean particle size reduces the likelihood of particle segregation of the percarbonate from other constituents of compact or ultra-compact or granulated xe2x80x9cconventionalxe2x80x9d detergent compositions. Advantageously, therefore, the combination is achieved of large particle size with small amount of coating to obtain excellent in pack stability and rapid dissolution.
Advantageously, it has been found that a number of preferred coated percarbonates according to the present invention have a heat emission at 40xc2x0 C. of below 4 xcexcW/g and preferably below 1.5 xcexcW/g in the beat emission test hereinafter described.
The present invention also relates to washing or bleaching compositions containing particulate coated sodium percarbonate, such as product according to the present invention described hereinabove and/or produced by the process according to the present invention hereinabove.
In many preferred washing compositions according to the present invention intended primarily for laundry washing, one or more of the composition components are selected within the following narrower bands:
percarbonate 2 to 40%, particularly 5 to 30%
surfactant 2 to 40%, particularly 5 to 25%
builder 1 to 60%, particularly 5 to 40%
diluent 1 to 70%, particularly 5 to 50%
additives 1 to 10% in total.
In many related bleach preparations, often intended for use in conjunction with detergent compositions containing little or no bleach, or as a bleach supplement to bleach containing compositions, such bleach preparations contain
percarbonate 5 to 90%, particularly 20 to 50%
surfactant 0 to 20%, particularly 0.5 to 5%
builder 1 to 95%, particularly 30 to 80%
diluent 1 to 95%, particularly 30 to 80%
additives 0 to 20% in total, preferably 1 to 10%.
The surfactants for incorporation in solid laundry or bleach compositions of the present invention can be selected from particulate or flaky anionic, cationic, non-ionic, zwitterionic, amphoteric and ampholytic surfactants and can be either natural or synthetic soaps. A number of suitable surfactants are described in chapter 2 of Synthetic Detergents by A Davidsohn and B M Milwidsky (6th edition) published in 1978 by George Godwin Ltd and John Wiley and Sons, incorporated herein by reference. Without limiting to these surfactants, representative sub-classes of anionic surfactants are carboxylic acid soaps, alkyl aryl sulphonates, olefin sulphonates, linear alkane sulphonates, hydroxy-alkane sulphonates, long chain and OXO alcohol sulphates, sulphated glycerides, sulphated ethers, sulpho-succinates, alkane sulphonates, phosphate esters, sucrose esters and anionic fluorosurfactants; representative classes of cationic surfactants include quaternary ammonium or quaternary pyridinium salts containing at least one hydrophobic alkyl or aralkyl group; representative classes of nonionic surfactants include condensates of a long chain alkanol with either polyethylene oxides or with phenols, or condensates of long chain carboxylic acids or amines or amides with polyethylene oxide, and related compounds in which the long chain moiety is condensed with an aliphatic polyol such as sorbitol or condensation products of ethylene and propylene oxides or fatty acid alkanolamides, polyalkylglucolides, glucosamides and fatty acid amine oxides; representative classes of amphoteric/zwitterionic surfactants include sulphonium and phophonium surfactants, optionally substituted by an anionic solubilising group. The proportion of surfactant, expressed as a fraction of all the surfactant present is often from {fraction (2/10)} to {fraction (8/10)}ths anionic, from 0 to {fraction (6/10)}ths non-ionic, and from 0 to {fraction (3/10)}ths for the other surfactants.
Detergent builders that are suitable for inclusion in compositions according to the present invention include specifically alkali metal phosphates, particularly tripolyphosphate but also tetrapyrophosphate and hexametaphosphate, especially the sodium salt of each, alkali metal, (preferably sodium) carbonates, alkali metal, (preferably sodium) borates, and siliceous builders including clays like bentonite, zeolites such as A, X, Y, AX and MAP zeolites (EP-A-O 552 053) and layered silicates such as the product available under the trade designation SKS6. The coatings achievable with the sucrose or like containing coating agents of the present invention render sodium percarbonate that has been so coated at higher levels particularly suited to incorporation in the relative aggressive detergent compositions, ie those containing aluminosiliceous builders. Mixtures of the zeolite builders either with each other and/or with other siliceous and/or phosphate and or carbonate and/or clay builders can be employed in the instant invention compositions. Useful detergent compositions can also include organic chelating builders as nitrilotrisodium triacetate (NTA), EDTA, EDTMP and DTPMP. Such chelating builders can be employed in a relatively small amount as an augmenting builder and peroxygen stabilizer, such as of 1 to 10%.
The detergent compositionscan also contain diluents, in an amount usually of not more than about 50% w/w. Such diluents include sodium and magnesium sulphate and are less favoured than previously by manufacturers of detergent compositions, who in recent years have promoted concentrated compositions and compositions having a higher bulk density.
Detergent compositions of the present invention can also contain other substances selected for dedicated purposes in detergent compositions, which in some instances are referred to collectively as detergent additives. Among such additives, the following can be mentioned: persalt activators, optical brighteners, foam inhibitors, enzymes, fading inhibitors and antiredeposition agents, colorants, pH regulators. Such aciditives for incorporation in persalt-containing detergent compositions have been described in greater detail in Chapter 4 and exemplified in Chapter 7 of the aforementioned work by Davidsohn and Mildwisky and are well known to skilled practitioners. Thus, for example, the bleach activator is typically a compound which generates a peroxyacid or an anion thereof by reaction with the percarbonate and is employed in a mole ratio of about 4:1 to 1:2 percarbonate: activator for monoactivating activators and proportionately for multi-activating activators. Peroxyacid-generating activators are usually N-acyl or O-acyl compounds and a peracid, often peracetic through to pernonanoic acid is generated by interaction between the compound and a perhydroxyl anion liberated from the percarbonate on its dissolution. Activators have become regular constituents of washing compositions intended for machine washing at low temperatures. A non-exhaustive range of activators a1 to a20 described below can be employed herein.
(a1) carboxylic acid or mixed carboxylic acid/sulphonic acid anhydrides such as benzoic anhydride, phthalic anhydride, bis(ethane sulphonic) acid, anhydride and benzene sulphonic acid/benzoic acid anhydride.
(a2) enol esters such as vinyl or isopropenyl acetate or benzoate or divinyl adipate.
(a3) gem diesters such as ethylidene or isopropylidene diacetate or dibenzoate, or ethylidene benzoate acetate or heptanoate, or bis(ethylidene acetate) adipate or azelate.
(a4) sugar esters such as glucose pentacetate or lactose octacetate.
(a5) carbonic acid esters such as alkali metal salts of para(ethoxycarbonyloxy) benzoic acid or para(propyloxy carbonyloxy) benzene sulphonic acid.
(a6) N,N-diacylated amines, such as N,N,Nxe2x80x2Nxe2x80x2-tetraacetyl (methylene or ethylene) diamine, N,N-diacetylaniline, N,N-diacetylmethylamine or N,N-diacetyl-p-toluidine.
(a7) Diacyiated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin.
(a8) Acylated glycolurils, such as tetraacetylglycoluril.
(a9) N-alkyl-N-sulphonylcarbonamides, such as the compounds N-methyl-N-mesylacetamide, N-methyl-N-mesyl-henzamide, N-methyl-N-mesyl-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide.
(a10) N-acylated cyclic hydrazides, acylated thiazoles or urazoles, such as monoacetylmaleic acid hydrazide.
(a11) Diacylated 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine.
(a12) Acylation products of propylenediurea or 2,2-dimethylpropylenediurea (2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonane-3,7-dione, or its 9,9-dimethyl derivative, especially the tetraacetyl- or the tetrapropionylpropylenediurea or their dimethyl derivatives.
(a13) O,N,N-trisubstituted hydroxylamines, such as O-benzoyl-N,N-succinyl-hydroxylamine, O-acetyl-N,N-succinyl-hydroxylamine, O-acetyl-N,N-phthaloyl-hydroxylamine, O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine and O,N,N-triacetylhydroxylamine.
(a14) N,Nxe2x80x2-diacyl-sulphurylamides, such as N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-diacetyl-sulphurylamide and N,Nxe2x80x2-diethyl-N,Nxe2x80x2-dipropionyl-sulphurylamide.
(a15) Sulphonyl halides such as p-(acetyl amino) phenyl sulphonvl chloride.
(a16) Azines such as diisocyanato-s-triazine or a halotriazine.
(a17) N-Sulphonylazoles.
(a18) N-acyl carboxylic imides such as N-acetyl caprolactam, N-acetyl diglycolimide, N-acetyl succinimide and N-acetyl phthalimide.
(a19) Mixed O-acyl, N-acyl compounds such as alpha-acetoxy-alpha-methyl-N,Nxe2x80x2-diacetoxymalonamide or O-acetyl-N,N-diacetylethanolamine.
(a20) Salts of benzenesulphonic acid esters of carboxylic acids such as sodium nonanoyloxybenzenesulphonate, sodium benzoyloxybenzenesulphonate or sodium isononanoyloxybenzenesulphonate.
The preferred activators include TAED, SNOBS, sodium isononoyloxybenzene sulphonate, TAGU and sugar esters. The weight ratio of percarbonate to activator is often from 1:1 to 10:1.
Another type of activator for washing/bleaching compositions comprises certain transition metal salts and/or complexes, for example certain manganese, cobalt, and titanium complexes, sometimes employed in conjunction with a calcium promoter, as described in European Patent Application-A-0 272 030. Commonly used optical brighteners include stilbene derivatives. Common antiredeposition agents include carboxymethyl cellulose and polyvinyl pyrrolidone.
The washing and/or bleaching compositions can be employed for washing and or bleaching operations, such as for washing domestic laundry by hand or using machines employing either top loading or front loading, and using either long or short ratios of liquor to laundry. Such machines can be operated in accordance with currently described operation conditions for respectively persalt or persalt plus activator containing compositions, including washing at cold soak temperatures, eg from about 10 to 30xc2x0 C., low temperature operation at from 30 to 60xc2x0 C. (both of which preferably with bleach activator) or at high temperatures eg of about 60xc2x0 C. up to boil wash. The detergent compositions can be dispensed in accordance with instructions on the container, such as direct dispensing into the wash solution for hand washing, or into the laundry before wetting for machine washing, or via a dispensing tray through which wash water is flushed or from a dispensing ball or sachet placed within the laundry.
By virtue of the excellent solubility of the invention coated percarbonate in aqueous wash solutions, and its excellent pack stability, and especially of the best combinations tested, the invention coated percarbonate not only enables excellent stain removal of bleachable stains to be effected, but it enables such performance to be retained to a substantial extent during a long period of time whilst the detergent is distributed, purchased by the eventual end user and stored by the user.
In further variations on compositions containing percarbonate according to the instant invention, the compositions are employed for washing dishes. Such dishwasher compositions often comprise by weight:
percarbonate 2 to 30%, particularly 5 to 20%
surfactant 0.5 to 30%, particularly 1 to 25%
builder 1 to 80%, particularly 10 to 60%
additives 1 to 50% in total, preferably 5 to 30%.
In the dishwasher compositions, the surfictants are often selected from ranges of surfactants contemplated for laundry formulations; but in an amount and with a preference for low foaming surfactants and/or the addition of sufficient foam suppressers to control to a minimum the extent of foaming within the dishwasher.
In the dishwasher compositions, the builders are normally selected from water soluble builders such as polycarboxylates, phosphates, silicates, carbonates and phosphonates such as those which have been described herein briefly for laundry detergents. Polycarboxylates are amongst the especially favoured builders. They can comprise acyclic, alicyclic aromatic or heterocylic carboxylic acids. Useful polycarboxylates are often monomeric or oligomeric and can comprise, amongst others, dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids. They can also be hydroxy-substituted. Suitable polycarboxylates can include aliphatic C4 to C6 xcex1-xcfx89 dicarboxylates, optionally unsaturated, citrates, citraconates, carboxymethyloxysuccinates, oxypolycarboxylates, ethane or propane tetacarboxylates and mellitate or pyromellitate. Other suitable polycarboxylates include tetracarboxylate derivatives of cyclopentadiene or tetrahydrofuran, polycarboxylate derivatives of hexane and carboxymethyl derivatives polyhydric alcohols, eg mannitol, xylitol or sorbitol.
The builder can desirably contain a small proportion (0.1 to 2%) of complexing builders such as polyphosphonates, eg hydroxyethanediphosphonate or polymethylenephosphonate derivatives of amines or polyamines such as ethylenediamine tetramethylene phosphonate or cyclohexane-1,2-tetramethylene phosphonate or diethylenetriamine pentamethylene phosphonate, as such or in acid form.
Amongst the additives, it is preferable to employ a bleach activator, such as a1) to a20) described hereinabove in the ratio to percarbonate and weight proportions in the composition described for laundry compositions. It is of practical benefit to employ a corrosion inhibitor in an amount of up to about 5%, preferably in addition to the various phosphate builders which may also be present and which can inhibit corrosion to a certain extent. Such additional corrosion inhibitors include benzotriazole and its derivatives, aromatic mercarptans and diols including lauryl mercaptan thiophenol, thionapthol, thioanthranol and thionalide. Other types of corrosion inhibitor include fatty carboxylic acids and their hydroxy-substituted counterparts, as such or as a watersoluble salt, hydroxyaromatic antioxidants and paraffin oils, preferably with molecular weight of about 350 to 600.
A further additive which can be present comprises an acidifier, preferably in an amount of 0.1 to 30% and particularly from 1 to 25%. The acidifier is often conveniently capable of acting as a builder when introduced into solution and is thus a carboxylic acid variation of the aforementioned carboxylate builders. Other suitable acidifiers include water soluble monocarboxylic acids such as lactic acid. It is preferable for the acidifier to be coated so as to delay release of the acidifier until a significant fraction of bleach activator has reacted with the percarbonate, generating the more active peracid species. Suitable coatings are often from about 3 to 10% by weight of poorly water-soluble compounds selected from hydrocarbon waxes, hydrogenated vegetable oils, fatty acids, amide derivatives or glycerides.
Coatings with a softening point around 40-50xc2x0 C. are often of interest.
Dishwasher compositions containing the invention coated percarbonate are normally provided in the form of granules or tablets obtained by conventional granulation of the powders preferably adding a percarbonate granule to preformed granules of the remaining detergent constituents or by compressing the constituents in a conventional method in a mould preferably in the presence of a typical tablet lubricant.
Processes for washing in automatic dishwashers are often conducted at a temperature in the region of about 40 to 70xc2x0 C.
Certain embodiments of the present invention are described hereinafter in greater detail by way of example only.
In the Examples and Comparisons except where specifically indicated coated sodium percarbonate was obtained by the following general process and tested where indicated by the following test procedures.
A solution of defined coating agent constituent(s) was prepared by stirring a specified weight of the (or each) constituent in a specified weight of demineralised water and heating to approximately 40xc2x0 C. if necessary until a clear solution without suspended solids was apparent to an experienced eye. A specified feedstock of particulate sodium percarbonate usually 1 kg was placed in a Lxc3x6dige M5R(trademark) mixer at laboratory ambient temperature and sufficientsolution was poured slowly onto the agitated particles to add the specified weight of coating agent. The agitation was continued for a further 2-3 minutes to transfer the solution substantially evenly across the bed of particles. The resultant damp particles were transferred into a laboratory scale (Aeromatic(trademark) STREA 1) fluid bed drier in which they were fluidized and dried by an updraft of hot dry air having a temperature at inlet of approximately 70xc2x0 C.-85xc2x0 C. and maintaining a bed temperature of 65-75xc2x0 C. for approximately 30 minutes. The particles were thereafter cooled briefly by an updraft of cool air to a bed temperature of about 40xc2x0 C. and were then available for a series of tests to determine the properties of the coated products.
F1 A feedstock obtained from a continuous wet process for precipitating percarbonate from aqueous solution in the presence of a chloride salting-out agent and having mean particle size of 764 xcexcm Avox of 13.2% and bulk density of 1.00.
F2 A second feedstock obtained from a continuous wet process for precipitating percarbonate from aqueous solution in the presence of a chloride salting-out agent and having mean particle size of 516 xcexcm, and Avox of 13.65%.
F3 A third feedstock obtained from a continuous wet process for precipitating percarbonate from aqueous solution in the presence of a chloride salting-out agent and mean particle size of 489 xcexcm, Avox of 13.8% and bulk density of 1.01.
F4 A fourth feedstock obtained from a continuous wet process for precipitating percarbonate from aqueous solution in the presence of a chloride salting-out agent and having mean particle size of 465 xcexcm, Avox of 14.2% and bulk density of 0.99.
F5 feedstock obtained from a continuous wet process for precipitating percarbonate from aqueous solution in the absence of a chloride salting-out agent having an Avox of 14.7%, mean particle size of 765 xcexcm and bulk density of 0.97.
F6 A feedstock obtained from a continuous wet process, or precipitating percarbonate from aqueous solution in the absence of a chloride salting-out agent having an Avox of 14.8%, mean particle size of 751 xcexcm and bulk density of 1.04.
The particle size distribution was obtained by sieving the material through a nest of 9 sieves with apertures ranging from 1400 down to 75 xcexcm. From the weight retained on each sieve, the weight fraction was determined, and from the distribution, the mean particle size was calculated.
The free flowing bulk density of the products was measured placing a sample in a cone of depth 60 mm, with top diameter 53 mm and base diameter 21 mm, the base being at a height of 20 cm above a work surface and allowed to flow under gravity into a collecting vessel on the work surface. The contents of the vessel are carefully leveled off by horizontal passage of a blade and weighed. The density is determined by comparison with the known volume of the vessel.
The solubility of the products listed in the Tables herein was determined according to the method adapted from international standard ISO 3123-1976 reported herein, by mixing the particulate product (2 g) with demineralised water (1000 g) maintained at 15xc2x0 C. and the electrical conductivity of the aqueous phase was monitored. Dissolution of the percarbonate resulted in an increase in conductivity, and the time taken to reach 90% of the maximum change was recorded in order to show how fast or slow the products would dissolve. This is the test by which the solubility of the claimed products herein is judged.
A 9 cm diameter petri dish with a 1 cm depth rim is weighed accurately on a 4 decimal place balance, (W1). A sample of dry sodium percarbonate (about 20 g) is placed on the petri dish which is gently agitated to generate an even particulate layer across the base of the dish and reweighed on the same balance, (W2). The sample on the petri dish is stored in a room, about 3 m high, wide and long in an atmosphere maintained for a period of 24 hours at 32xc2x0 C. by a thermostat controlled heater and at 80% Relative Humidity (RH) by introduction of a fine droplet water spray under the control of a humidity detector and weighed on the same balance, (W3). The samples are protected by a shield from the spray.
The moisture pick-up of the sodium percarbonate is calculated as follows:       Moisture              xe2x80x83            Pick              xe2x80x83            up              xe2x80x83                  (              g                          /                        kg            )        =            1000      xc3x97              (                  W3          -          W2                )                    (              W2        -        W1            )
The extent of moisture pick-up is indicative of the capability of the. product to extract moisture from its immediate environment, and thus of the stability of the product when exposed to humid conditions, for example those which can be generated in detergent or bleach/additive compositions containing substances like molecular sieves that are capable of absorbing and releasing a significant proportion of moisture.
In the Tables, this is indicated by MPU.
This was measured by transferring a sample of the percarbonate into a microcalorimeter, model LKB 2277, also called a Thermal Activity Monitor which is marketed by Thermometric Limited, Sweden in which a temperature of 40xc2x0 C. is maintained. The heat from the sample over a standard period of 16 hours is measured. In the Tables, this measurement is indicated by LKB40. This is the test by which the heat emission of the claimed products herein is judged.
A low reading indicates an intrinsically stable product, ie before the product is contacted with detergent composition or any other diluent.
Avox herein was measured by dissolving a weighed sample (about 0.2 g) in about 100 mls of 10% w/w sulphuric acid and titrating the solution against standard potassium permanganate solution.
The storage stability of the products was tested in one of two general methods.
In a rapid method, 50 parts by weight of percarbonate was blended with 50 parts by weight of a detergent constituent, specifically a detergent builder, Zeolite 4A powder obtained from Aldrich Chemicals to give an even distribution and its available oxygen (Avox) measured. The blend was stored in an open beaker housed in a constant environment chamber at 32xc2x0 C./80% relative humidity and samples were taken after specified periods of storage and analyzed for residual Avox. A comparison of the Avox before and after storage is a demonstration of the stability of the product.
This method for determining percarbonate stability is referred to in the Tables as xe2x80x9cAvox Recovery Rapidxe2x80x9d.
In a second method, usually conducted over periods of weeks, 15 parts by weight of percarbonate was blended with 85 parts by weight of one of the detergent compositions indicated below and 50 g samples housed in small sealed polyethylene coated cardboard cartons (Howarth Packaging) with moisture permeability of 65.31 g mxe2x88x922 dayxe2x88x921, measured at 32xc2x0 C./80% relative humidity. The cartons were stored in a constant environment chamber at 32xc2x0 C./80% relative humidity and the Avox content after storage was compared with that before storage.
The reference percarbonate free compositions blended with the coated percarbonate (to obtain compositions according to the present invention) were as follows:
The long term test for percarbonate, in which it was mixed with detergent A and stored in small polyethylene coated cartons, is the stability test by which the claimed products is judged.
Bleach-free detergent base of a commercially available laundry detergent composition containing zeolitie 4A builder
Bleach-free detergent base of a second commercially available laundry detergent composition containing zeolite 4A builder
The method of determining the stability of the percarbonate during storage mixed with one of the Reference Detergents is referred to in Tables herein as xe2x80x9cAvox Recovery Det A, B or C, as the case may be. The stability is expressed in terms of the proportion of Avox remaining after storage for 6 weeks, unless otherwise stated.

Process for stabilizing particulate alkali metal percarbonate