WO1998035010A1

WO1998035010A1 - Particulate bleach additive composition for use in granular detergent compositions

Info

Publication number: WO1998035010A1
Application number: PCT/US1998/002528
Authority: WO
Inventors: Robert Louis Bill; Scott William Capeci
Original assignee: The Procter & Gamble Company
Priority date: 1997-02-10
Filing date: 1998-02-09
Publication date: 1998-08-13

Abstract

A particulate bleach additive composition for use in granular detergent products is provided. The particulate additive composition includes: (a) from about 1 % to about 90 % by weight of carrier particles; (b) from about 1 % to about 70 % by weight of a liquid bleach activator compound having formula (I), wherein R1 is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C1-C8 linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group; and (c) from about 1 % to about 75 % of a liquid binder. The bleach activator and the liquid activator are coated in and onto the carrier particles.

Description

PARTICULATE BLEACH ADDITIVE COMPOSITION FOR USE IN GRANULAR DETERGENT COMPOSITIONS

TECHNICAL FIELD The invention generally relates to a particulate bleach additive composition, and more particularly, to a composition containing unsymmetrical acyclic imide bleach activators in particulate form for easy incorporation into granular detergent compositions. The particulate bleach additive composition is particularly useful in laundry, automatic dishwashing and hard surface cleaning compositions. BACKGROUND OF THE INVENTION The formulation of bleaching compositions which effectively removes a wide variety of soils and stains from fabrics under wide-ranging usage conditions remains a considerable challenge, especially in the laundry detergent industry. Challenges are also faced by the formulator of hard surface cleaning compositions and automatic dishwashing detergent compositions (ADD's), which are expected to efficiently cleanse and sanitize dishware, often under heavy soil loads. The challenges associated with the formulation of truly effective cleaning and bleaching compositions have been increased by legislation which limits the use of effective ingredients such as phosphate builders in many regions of the world.

Oxygen bleaching agents, such as hydrogen peroxide, have become increasingly popular in recent years in household and personal care products to facilitate stain and soil removal. Bleaches are particularly desirable for their stain- removing, dingy fabric cleanup, whitening and sanitization properties. Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, in automatic dishwashing products and in hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include color damage on fabrics and surfaces. In addition, oxygen bleaching agents tend to be extremely temperature rate dependent. Thus, the colder the solution in which they are employed, the less effective the bleaching action. Temperatures in excess of 60°C are typically required for effectiveness of an oxygen bleaching agent in solution. To solve the aforementioned temperature rate dependency, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the stained or soiled substrate material. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of from about 40°C to about 60°C. In water temperatures of less than about 40°C, the peroxyacid compound loses some its bleaching effectiveness.

Numerous substances have been disclosed in the art as effective bleach activators. One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on hydrophobic stains, e.g. dingy, yellow stains such as those resulting from body oils. Another type of activator, such as non- anoyloxybenzenesulfonate (NOBS) and other activators which generally comprise long chain alkyl moieties, is hydrophobic in nature and provides excellent performance on dingy stains. However, many of the hydrophobic activators developed demonstrate limited performance on hydrophilic stains. The search, therefore, continues for more effective activator materials, especially for those which provide satisfactory performance on both hydrophilic and hydrophobic soils and stains. Improved activator materials should be safe, effective, and will preferably be designed to interact with troublesome soils and stains. Various activators have been described in the literature. Many are esoteric and expensive. It has now been determined that certain selected bleach activators are unexpectedly effective in removing both hydrophilic and hydrophobic soils and stains from fabrics, hard surfaces and dishes. When formulated as described herein, bleach additive and bleaching compositions are provided using the selected bleach activators to remove soils and stains not only from fabrics, but also from dishware in automatic dishwashing compositions, from kitchen and bathroom hard surfaces, and the like, with excellent results.

Unfortunately, such bleach activators are produced in liquid form and simply spraying the liquid bleach activator onto laundry or dishwashing granules is difficult for several reasons. First of all, some liquid bleach activators are relatively viscous in nature which leads to "clogging" or otherwise difficult transitions through spray nozzles, which thereby prevents adequate incorporation into the detergent product. Additionally, spraying the liquid bleach activator ultimately leads to physical property problems in that the detergent granules have a strong tendency to "cake" upon being subjected to liquid activators. This obviously leads to poor product appearance and consumer acceptability since the "caked" product is difficult to dispense during use.

Furthermore, spraying the liquid activator onto detergent granules deposits the activator on the outer surface of the granules which is readily exposed to the moisture in the atmosphere, especially when the product is stored for extended periods of time prior to use. The exposure to moisture or water prior to use renders the bleach activator compound unstable, and therefore, reduces its effectiveness when ultimately used. This decreased shelf-life as a result of spraying the liquid activator onto the detergent composition is extremely undesirable and can have detrimental commercial effects on the product in which the activator is contained. Attempts at embodying such liquid activators in particulate form have also failed in that the activity of the activator is not retained due to particles susceptibility to moisture. Additionally, embodying these liquid activators in particulate form at very high active levels has been difficult, as well.

Accordingly, it would be desirable to have a bleach activator additive which provides satisfactory performance on both hydrophilic and hydrophobic soils and stains, and which is safe, effective, and designed to interact with troublesome soils and stains. Importantly, it would be desirable to have a bleach additive composition having improved physical properties and performance even when incorporated into fully formulated detergent compositions.

BACKGROUND ART Bleach activators of various types are described in U.S. Patents 3,730,902;

4,179,390; 4,207,199; 4,221,675; 4,772,413; 5,106,528; European Patent 063,017; European Patent 106,584; European Patent 163,331; Japanese Patent 08/27487 and PCT Publication W.O. 94/18298. Imide Compounds of various types are disclosed in U.S. Patents 4,745,103 and 4,851,138. A process for preparing diimides is described in U.S. 3,899,509.

SUMMARY OF THE INVENTION The invention meets the aforementioned needs by providing a particulate bleach additive composition containing an unsymmetrical acyclic imide bleach activator compound (e.g. N-Methyl N-Nonyl Aceta ide or "NMA") which has optimum performance and physical properties. The particulate bleach additive composition can be incorporated into granular detergent compositions without detrimentally affecting the physical properties or the activity of the unsymmetrical acyclic imide bleach activator compound contained therein.

In accordance with one embodiment of the invention, a particulate bleach additive composition is provided. The particulate additive composition comprises: (a) from about 1% to about 90% by weight of carrier particles; (b) from about 1% to about 70% by weight of a liquid bleach activator compound having the formula

wherein R\ is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C 1 -Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C1 -C4 linear or branched chain saturated or unsaturated alkyl group; and (c) from about 1% to about 75% of a liquid binder. The bleach activator and the binder are coated in and onto the carrier particles. By coated "in" the carrier particles, it is meant that the bleach activator and binder are contained on the inner surfaces of the particles created by the intraparticle void space. In another embodiment of the invention, a particulate bleach additive composition is provided. This particulate bleach additive composition comprises: (a) from about 1% to about 90% by weight of carrier particles; (b) from about 1% to about 70% by weight of a liquid bleach activator compound having the formula

wherein R\ is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a Cj-Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group; and (c) a binder system including (i) from about 0.5% to about 15% of C12-13 linear alkylbenzene sulfonate surfactant, (ii) from about 1% to about 25% of polyethylene glycol, (iii) from about 0.5% to about 10% of pelargonic acid, and (iv) from about 1% to about 25% of palmitc acid. The bleach activator and the binder are coated in and onto the carrier particles.

In yet another embodiment of the invention, a detergent composition is provided. This detergent composition comprises: (a) detergent granules containing a detersive surfactant and a builder; and (b) a particulate bleach additive composition including, by weight of the additive composition, (i) from about 1% to about 90% of carrier particles; (ii) from about 1% to about 70% of a liquid bleach activator compound having the formula

wherein R\ is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a Ci-Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group; and (iii) from about 1% to about 75% of a liquid binder Die bleach activator and the binder are coated in and onto the carrier particles. The invention also provides a method of laundering soiled fabrics comprising the steps of contacting the fabrics in an aqueous medium with an effective amount of a detergent composition as described herein. Accordingly it is an object of the present invention to provide a bleach activator additive which provides satisfactory performance on both hydrophilic and hydrophobic soils and stains, and which is safe, effective, and designed to interact with troublesome soils and stains. It is also an object of the invention to provide such a bleach additive so that physical properties of the compositions in which it is contained are acceptable and the activity of the activator is retained prior to use. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS One aspect of the invention involves a particulate bleach additive composition that unexpectedly possesses superior performance and physical properties even when incorporated into fully formulated detergent compositions. It is essential for the bleach additive composition to include carrier particles and a liquid bleach activator. The binder can include one or more of several ingredients as detailed hereinafter. The invention also provides detergent compositions used in laundry or dishwashing applications which include the particulate bleach additive composition of the invention. Such detergent compositions typically include granules containing a detersive surfactant and a builder. Preferably, the detergent compositions will also include a source of hydrogen peroxide as detailed more particularly hereinafter.

Carrier Preferably, the carrier particles are selected from the group consisting of silicas, aluminosilicates and mixtures thereof. Particularly preferred carrier particles are precipitated silica particles and amorphous aluminosilicate particles. Most preferably, the carrier is precipitated silica particles which are commercially available from Huber Corporation under the trade name Zeothix 265. The precipitated silica particles preferably have a median particle size of from about 0.5 microns to about 10 microns. It should be understood that a wide variety of particulate carrier materials can be used beyond those specifically mentioned herein without deviating from the scope of the invention.

Binder System The additive composition requires a binder to be employed which is a hydrophilic material that is capable of binding particles together, and preferably in liquid form. Although many liquid hydrophilic materials having such "binding" properties are available and suitable for use in the current process, one convenient option is to use one of the various readily available surfactants. Such surfactants include anionic surfactants such as linear alkylbenzene sulfonate and nonionic surfactants such as alkyl ethoxylated sulfates. Overall, the binder provides a moisture and alkalinity barrier for the particulate bleach additive composition such that it does not degrade prior to use.

Optionally, other ingredients can be included with the liquid hydrophilic material to form a "binder system" for enhancing the physical properties of the particulate bleach additive composition. In such cases the binder system may employ an ingredient to "crispen" or otherwise impart hardness to the particles, such as polyethylene glycol, polyvinylpyrrolidone (PVP), polyvinylpyridine N-oxide (PVNO) or Copolymers of N-vinylpyrrolidone and N-vinylimidazole (PVPVI). Another optional ingredient is an acidic coating which protects the bleach activator in the bleach additive composition from degradation as a result of exposure to alkalinity. Although virtually any acidic material capable of being coated onto the carrier particles can be used, the preferred ingredient is palmitic acid. Another similar material which is suitable for use herein is citric acid. Additionally, an ingredient which reduces friability or "chipping" of the resultant particulate bleach additive composition may be included. Such ingredients include, but are not limited to pelargonic acid, and C_j2_i3 linear alkylbenzene sulfonate.

In preferred embodiments, the binder includes only from about 0.5% to about 15%, preferably from about 1.5% to about 10%, and most preferably from about 2.5% to about 6.0%, by weight of the bleach additive composition, of Cj2-13 linear alkylbenzene sulfonate surfactant. In more preferred embodiments of the bleach additive composition, the binder will be a "system" which includes from about 1% to about 25%, preferably from about 3% to about 20%, and most preferably from about 5% to about 12%, by weight of the bleach additive composition, of polyethylene glycol (Molecular Weight = 4000). The preferred binder system may also include from about 0.5% to about 10%, preferably from about 1% to about 10%, and most preferably from about 2% to about 5%, by weight of the bleach additive composition, of pelargonic acid. Another ingredient in the preferred binder system is from about 1% to about 25%, preferably from about 3% to about 20%, and most preferably from about 5% to about 12%, by weight of the bleach additive composition, of palmitic acid.

Bleach Activator The unsymmetrical acyclic bleach activators employed in the invention are unsymmetrical' acyclic imide bleach activators. The unsymmetrical acyclic imide activators used in the present invention have the formula: (I)

wherein R_] is a C7-C 13 linear or branched chain saturated or unsaturated alkyl group, R2 is a Cj-Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C 1-C4" linear or branched chain saturated or unsaturated alkyl group.

Preferred activators are those in which the R\ is a C7-C _{] j} linear or branched saturated alkyl group, more preferably, R\ is a C7-C 1 1 saturated alkyl group, R2 is a C1-C4 linear or branched saturated alkyl group and R3 is a C1 -C4 linear or branched chain saturated or unsaturated alkyl group. More preferably, R2 and R3 are C \ -C4 linear saturated alkyl groups and even more preferably are the same.

Further preferred activators according to the present invention are the N- alkanoyl-N-methyl acetamides. The activators have the formula (I) wherein both R2 and R3 are methyl groups. Thus, N-alkanoyl-N-methyl acetamides have the formula:

(II) O O

Rl ^N Me I Me where Ri is C7-C1 1 linear saturated alkyl group. Particularly preferred are N- octanoyl-N-methyl acetamide (when Ri is C7), N-nonanoyl-N-methyl acetamide (when R\ is Cg), N-decanoyl-N-methyl acetamide (when Ri is CQ) and N-dodecanoyl-N- methyl acetamide (when R\ is C_j 1 ).

While not wishing to be bound by theory, it is believed that as the number of carbons in the activators of formula (I) increases, the solubility of the compound decreases. Thus, as the activators of the present invention are ideally soluble for optimum performance of the activators, it is preferred that the number of carbon atoms in the activator compound be such that the activator compound displays satisfactory solubility profiles. In the present invention, the sum of the carbons in Ri , R2 and R3 is preferably less than 19 and more preferably less than 15. The unsymmetrical acyclic imide bleach activators used in the present invention provide superior bleaching ability and performance over the bleach activators of the prior art. While not wishing to be bound by theory, it is believed that the unsymmetrical acyclic imide bleach activators of the present invention provide both hydrophobic and hydrophilic bleaching agents in aqueous solutions. This is believed to be due to the fact that perhydrolysis can occur at either of the carbonyl groups in the activator. Thus, any molecule of the activators of formula (I) would undergo perhydrolysis in an aqueous solution to form either a bleaching agent (R_]C(0)OOH) having hydrophobic properties and a bleaching agent (R3C(0)OOH) having hydrophilic properties when R\ and R3 are defined as above. The bleaching agent may of course be protonated or deprotonated depending upon the in-use pH. A bleaching solution will then include both the hydrophilic bleaching agent and the hydrophobic bleaching agent. Thus, the bleaching capabilities of a mixed activator system (hydrophobic and hydrophilic) and even increased performance can be achieved through the use of a single bleach activator. Elimination of mixed activator systems may provide enormous potential benefits by eliminating the significant expense of an additional bleach activator. Furthermore, while not wishing to be bound by theory, it is believed that the bleach activators of formula (I) are liquids at or above room temperature.

Process The process of the instant invention involves producing a particulate bleach additive composition via initially blending a liquid bleach activator with carrier particles to form a powder which contains the bleach activator. Preferably, the carrier particles are comprised of a particulate carrier material selected from the group consisting of silicas, aluminosilicates and mixtures thereof. Particularly preferred carrier particles are precipitated silica particles and amorphous aluminosilicate particles. Most preferably, the carrier particles are precipitated silica particles which are commercially available from Huber Corporation under the trade name Zeothix 265. The precipitated silica particles preferably have a median particle size of from about 0.5 microns to about 10 microns. It should be understood that a wide variety of particulate carrier materials can be used beyond those specifically mentioned herein without deviating from the scope of the invention. The blending step can be carried forth in any conventional stirred vessel such as a Cuisinart Food Processor, Eirich Type R Mixer, Lodige CB or KM mixer. A preferred embodiment of the process entails mixing the liquid bleach activator and carrier particles in a weight ratio of from 1 : 10 to about 10: 1, preferably at a weight ratio of about 1 : 1. In the next step of the process, the powdered activator is either granulated or agglomerated with a binder to form the particulate bleach additive composition. The binder as well as the liquid bleach activator are detailed hereinafter. A preferred embodiment of the process entails mixing the binder and powdered activator in a weight ratio of from 1 : 10 to about 5: 1, preferably at a weight ratio of about 1 :3. If the powdered activator is granulated, the granulation step of the process can be carried forth in a dome granulator, e.g. commercially available from LCI Coφoration under the trade name Laboratory Dome Granulator Model DG-L1. Other granulation equipment which can be used include extruders, extructors, roll compactors and the like. Optionally, the process may include a spheronization step following the granulation step to "round" the particles, and thereby improve the flow properties of the resulting particulate bleach additive composition. Such an optional process step may be carried forth in equipment commercially available from LCI Corporation sold under the trade name Marumerizer. In the event that the powdered activator is agglomerated, the agglomeration step can be carried forth in equipment including but not limited to Eirich R type mixers commercially available from Eirich Machines, Inc., Schugi Granulators available from Hosokawa Bepex and sold under the trade name Flex-O-Mix, mixer/densifiers available from Lδdige (Germany) sold as Lodige CB or KM mixers, e.g., Lδdige CB 30 Recycler. One or a combination of these agglomeration apparatus may be used depending upon the degree of agglomeration desired. The various operating parameters involved in operating such equipment is discussed in U.S. Patent Nos. 5,366,652, 5,486,303, 5,489,392, 5,554,587 and 5,516,448, all of which are issued to Capeci et al and are incorporated herein by reference.

Generally speaking, the residence time of the powdered activator in both the granulation step and the agglomeration step will be from about 0.2 minutes to about 15 minutes. As those skilled in the art will appreciate, the residence time will vary depending upon the actual number of granulating or agglomerating mixers used and the other operating parameters of the equipment. For example, the temperature of the liquid activator is preferably from about 50°C to about 70°C, and the binder is added while preferably at from about 65°C to about 95°C. In this way, a particulate bleach additive composition having unexpectedly superior flow properties and performance is produced which can be admixed with other detergent compositions such as those used in conventional laundering operations.

Optionally, one or more additional process steps may be used in the process invention to enhance the properties of the particulate bleach additive composition. For example, the granulated or agglomerated bleach additive produced may be dried in a conventional fluid bed dryer or other known drying apparatus. In addition to this step or alternatively, the particulate bleach additive composition may be cooled in a fluid bed cooler. Both of these optional processing steps enhance the physical properties of the particulate bleach additive compositions.

Also, it may be beneficial to include a premixing step during which the liquid bleach activator is mixed with a liquid h>drophilic material so as to enhance the solubility of the bleach activator in the aqueous washing solution to which it is ultimately added. Although many liquid h>drophilic materials are suitable for use herein, one convenient liquid would be a nonionic surfactant.

Additionally, it may be beneficial to target the median particle size of the bleach additive composition so as to facilitate incorporation into fully formulated detergent products and/or further impros e ph> sical properties such a free flow and reduce particle size segregation during storage. In this vain, it is preferable for the median particle size to be in a range from about 500 microns to about 1000 microns, and most preferably from about 700 microns to about 800 microns. This can be accomplished by conventional sieving and grinding (for the oversized particles) and recycling (for the undersized particles) processing steps.

" In a typical detergent-manufacturing process, the admixed ingredients such as the particulate bleach additive composition produced by the present invention are incorporated after the base granules and/or agglomerates containing the common ingredients are formed. By way of example, detergent granules can be formed in a spray-drying tower which contain a detersive surfactant and builder to which liquid adjunct ingredients such as perfumes, some enzymes, some optical brighteners and the like are added via spraying. Thereafter, the dry admixed ingredients such as the particulate bleach additive composition are admixed with the fully formulated detergent composition. Such a process is also envisioned by the instant process invention.

Granular Detergent Compositions The particulate bleach additive compositions of the invention can be incorporated into fully formulated laundry, hard surface cleaning, and automatic dishwashing compositions. The particulate bleach additive of the present invention as described above are generally employed in combination with a source of hydrogen peroxide in the fully formulated compositions. Levels of particulate bleach additive in the fully formulated compositions may vary widely, e.g., from about 0.1% to about 90%, by weight of the composition, although lower levels, e.g., from about 0.1% to about 30%, or from about 0.1% to about 20% by weight of the composition are more typically used.

The source of hydrogen peroxide herein is any convenient compound or mixture which under consumer use conditions provides an effective amount of hydrogen peroxide. Levels may vary widely and are typically from about 0.1% to about 70%, more typically from about 0.2% to about 40% and even more typically from about 0.5% to about 25%, by weight of the bleaching compositions herein. The source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Mixtures of any convenient hydrogen peroxide source can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. The source of hydrogen peroxide and unsymmetrical bleach activator are typically at a ratio of from about 1 :3 to about 20: 1, as expressed on a basis of peroxide:activator in units of moles H2O2 delivered by the hydrogen peroxide source to moles bleach activator.

Fully formulated compositions including the particulate bleach additive composition, particularly those for use in laundry and automatic dishwashing, typically will also comprise other adjunct ingredients to improve or modify performance. Typical, non-limiting examples of such ingredients are disclosed hereinafter.

Adjunct Ingredients Adjunct ingredients can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the fully formulated composition in which the particulate bleach additive composition of the invention is included. Usual detersive surfactants, builders and other adjuncts for detergent compositions are included in U.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which can also be included in their conventional art- established levels for use (generally from 0% to about 20% of the detergent ingredients, preferably from about 0.5% to about 10%), include other active ingredients such as bleach catalysts, enzymes, enzyme stabilizers, color speckles, anti-tarnish and/or anti- corrosion agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, dyes, solubilizing agents, clay soil removal/anti- redeposition agents, carriers, processing aids, pigments, fabric softeners, static control agents, solid fillers for bar compositions, etc.

Dye transfer inhibiting agents, including polyamine N-oxides such as polyvinylpyridine N-oxide can be used. Dye-transfer-inhibiting agents are further illustrated by polyvinylpyrrolidone and copolymers of N-vinyl imidazole and N-vinyl pyrrolidone. If high sudsing is desired, suds boosters such as the C 1 n-C j alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The Cιø-C_]4 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSθ4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.

The present invention will now be described by reference to the following examples. Of course, one of ordinary skill in the art will recognize that the present invention is not limited to the specific examples herein described or the ingredients and steps contained therein, but rather, may be practiced according to the broader aspects of the disclosure.

EXAMPLE I a. Preparation of n-Methyl Nonanoyl Amide A 50 L, 3-necked round-bottomed flask equipped with a 2 L pressure equalizing addition funnel, mechanical stirrer, argon inlet, thermometer, and reflux condenser is charged with methylamine (40 wt% in water, 8 L, 93 mol, 2.5 eq) and cooled in an ice/methanol bath to 10 °C. Nonanoyl chloride/diethyl ether (approximately 1 : 1 volume ratio) is mixed in the addition funnel and added to the aqueous methylamine at a rate slow enough to maintain reaction temperature below 30 °C. The reaction is stirred slowly enough to allow the organic and aqueous layers to remain separate. Upon complete addition of the initial nonanoyl chloride/diethyl ether, 2 L of diethyl ether is added directly to the reaction. Nonanoyl chloride/diethyl ether is then added in higher ratio until 6.59 kg (37.3 mol) of nonanoyl chloride and 14 L of diethyl ether has been added. The stirred reaction is allowed to slowly warm to room temperature overnight.

Distilled water (2 L) is added and the reaction is stirred vigorously. The aqueous layer is removed and discarded. The organic layer is then washed with saturated sodium bicarbonate solution and dried over magnesium sulfate. Solvent is removed under reduced pressure to give a white solid. b. Preparation of N-nonanoyl-N-methylacetamide (NMA)

A 100 mL three-necked, round bottomed flask equipped with a short path distillation apparatus with vacuum adapter, Vigreaux column, and pressure equalizing addition funnel is charged with acetic anhydride (14.9 g, 146 mmol) and N- methylnonanamide (2.5 g, 14.6 mmol). The reaction mixture is heated (65° C) and three drops (ca. 0.07 g, .7 mmol) of H2SO4 (cone) is added. Aspirator vacuum is applied to remove acetic acid formed from the reaction mixture. Additional acetic anhydride (ca. 18 g) is added to replace that which has been reacted and removed. Upon completion of the reaction the remaining acetic anhydride/acetic acid is removed under reduced pressure. The residue is purified by Kugelrohr distillation (100° C, 0.35 mm Hg) to give a water white oil.

EXAMPLE II a. Preparation of n-Methyl Nonanoyl Amide Under nitrogen pressure, 20.39 lbs. of liquid monomethyl amine (MMA) is pushed into a 25 gallon agitated pressure vessel. The pressure vessel is held at a pressure of about 25-40 PSIG after MMA addition. The vessel's agitator is started. 51.95 lbs. of pelargonic acid is added to the vessel over a 0.5 to 1 hour period through a diaphragm pump. The reactor temperature rises to about 60- 100 F and 50- 100 PSIG during acid addition. When all of the acid is in the reactor, heating is started while agitation continues. The reactor is raised to 325-330 °F . The pressure rises to about 350 PSIG during this heatup process. The reactor is held at this temperature for 7 hours. Samples are taken hourly during this period and analyzed by gas chromatography. Final n-methyl nonanoyl amide content is above about 97%. Free pelargonic acid is less than about 3 %. At the end of 7 hours the reactor, while at 325-330 °F, is vented slowly to a sulfuric acid scrubber tank where the excess MMA is neutralized. The reactor is cooled to 122 °F and the resulting amide pressured out of the tank through a line to a 100 gallon glass lined reactor. b. Preparation of n-Methyl n- Nonyl Acetamide (NMA)

The remaining MMA and water that resulted from the amidation reaction are removed in the glass lined reactor at 122 °F and less than about 10 mm Hg vacuum. The reactor pressure is set at 100 mm Hg and 335.1 lbs. acetic anhydride is pulled in from a drum on a weigh scale via a Teflon lined stainless steel hose. The reactor is returned to atmospheric pressure by breaking vacuum with nitrogen. Heating and agitation are continued. The reactor is heated to 248 °F and sampled hourly and the samples analyzed by gas chromatography (GC). After approximately 10 hours conversion to crude NMA is 87.2%.

Crude composition : GC Area %

Di C2 Imide 1.929

C2/C9 Mixed Anhydride 6.377 n-Methyl n-Nonanoyl Amide 1.669 iso Co NMA 0.900

Linear C9 NMA 86.301

Di C9 Anhydride 0.105

Di C9 Imide 0.617

Other 2.102 c. NMA Isolation

Excess acetic anhydride is removed in the 100 gallon reactor at 122 °F and less than about 10 mm Hg vacuum. After the acetic anhydride is removed vacuum is broken with nitrogen.

A wash mixture made up of 95 lbs. of water 10 lbs. of sodium bicarbonate, and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled for 1 hour. The bottom layer is drained off. A second wash mixture consisting of 95 lbs. water, 6 lbs. sodium bicarbonate, 4 lbs. sodium carbonate and 35 lbs. of methanol is prepared. This mixture is added to the reactor, stirred for 1 hour and settled for 1 hour. The bottom layer is drained off. The product is washed a third time with 140 lbs. of pure water. The bottom layer is drained off. The product is then fractionally distilled in the reactor at pressure less than 10 mm Hg.

Final purity of the NMA is > 95% combined iso and linear NMA. The yield as compared to theoretical based on pelargonic acid is greater than about 75%.

EXAMPLE III Granulation Process 6.2 kg of NMA bleach activator made according to Example II is premixed with 4.2 kg of nonionic surfactant (Neodol 25-7 available from Shell Chemical Co.) to form the liquid activator mixture. 7.5kg of precipitated silica carrier particles commercially available from Huber Corporation under the trade name Zeothix 265 is charged to a Eirich R08 mixer. The Eirich mixer is operated at low speed (Pan - 28 rpm, Rotor - 600 RPM) for about 1 minute while the liquid activator mixture is added, after which the mixing is allowed to continue until a powdered activator is formed. A binder, which includes 1.9 kg of polyethylene glycol (M.W. = 4000, available from BASF), 1.0 kg of Ci2-]3 linear alkylbenzene sulfonate surfactant flakes (LAS flakes, available from Pilot Chemicals), 1.9 kg of palmitic acid (available from Witco Corp.), and 0.8 kg of nonanoic acid (available from Hoescht Celanese), is preformed. The binder and powdered activator are then charged into a Dome Granulator commercially available from LCI Corporation and sold under the trade name Laboratory Dome Granulator DG- Ll . The Dome Granulator is operated at low speed (15 rpm) until bleach additive granules having a median particle size of from about 41 1 to 1 130 microns are formed. The bleach additive agglomerates formed have the following formula: Bleach Additive Component % Weight

NMA bleach activator 26.5%

Nonionic surfactant 17.6%

Silica (precipitated) 32.0%

Binder

Polyethylene glycol (MW 4000) 8.2%

LAS flakes 4.2%

Palmitic acid 8.2%

Nonanoic acid 3.3%

100.0% The above exemplified particulate bleach additive composition unexpectedly has superior bleach boosting performance as well as physical properties alone and when incorporated into fully formulated detergent compositions. EXAMPLE IV

Agglomeration Process

6.2 kg of NMA bleach activator made according to Example II is premixed with 4.2 kg of nonionic surfactant (Neodol 25-7 available from Shell Chemical Co.) to form a liquid activator mixture. 7.5 kg of precipitated silica commercially available from Huber Corporation under the trade name eothix 265 is charged to an Eirich mixer commercially available from Eirich Machines Inc. and sold under the trade name Eirich R08. The Eirich mixer is operated at low speed (Pan - 28 rpm, Rotor - 600 RPM) for about 1 minute while the liquid activator mixture is added, after which the mixing is allowed to continue until a powdered activator is formed. A binder, which includes 1.9 kg of polyethylene glycol (M.W. = 4000, available from BASF), 1.0 kg of C 12-13 linear alkylbenzene sulfonate surfactant flakes (LAS flakes, available from Pilot Chemicals), 1.9 kg of palmitic acid (available from itco Corp.), and 0.8 kg of nonanoic acid (available from Hoechst Celanese), is premixed. The powdered activator and binder agglomerated in the same or a second Eirich R08 until bleach additive agglomerates having a median particle size of from about 41 1 to 1 130 microns are formed.

The bleach additive granules formed have the following formula: Bleach Additive Component % Weight

NMA bleach activator 26.5%

Nonionic surfactant 17.6%

Silica (precipitated) 32.0%

Binder

Polyethylene glycol (MW 4000) 8.2%

LAS flakes 4.2%

Palmitic acid 8.2%

Nonanoic acid 3.3%

100.0% The above exemplified particulate bleach additive composition unexpectedly has superior bleach boosting performance as well as physical properties alone and when incorporated into fully formulated detergent compositions.

EXAMPLE V Bleaching compositions having the form of granular laundry detergents are exemplified by the following formulations. COMPONENT A B C D

Bleach Additive* 5.0 3.5 1.0 3.5 2

Sodium Percarbonate 19.0 21.0

Sodium Perborate monohydrate 21.0 20.0

Sodium Perborate tetrahydrate 12.0 21.0

Tetraacetylethylenediamine 1.0

Nonanoyloxybenzenesulfonate 3.0

Linear alkylbenzenesulfonate 5.5 1 1.0 19.0 12.0 9.5

Alkyl ethoxylate (C45E7) 4.0 3.0 4.0 6.0

Zeolite A 20.0 20.0 9.5 17.0 21.0

SKS-6® silicate (Hoechst) 1 1.0 1 1.0

Trisodium citrate 5.0 5.0 2.0 3.0 3.0

Acrylic Acid/Maleic Acid 4.0 4.0 5.0 copolymer Sodium polyacrylate 3.0 3.0

Diethyienetriamine penta(methylene 0.4 0.4 phosphonic acid)

DTPA 0.4 0.4

EDDS 0.3

Carboxymethy Ice 1 lu lose 0.3 0.4

Protease 1.4 0.3 1.5 2.4 0.3

Lipolase® (Novo) 0.4 0.2

Carezyme® (Novo) 0.1 0.2

Anionic soil release polymer 0.3 0.4 0.5

Dye transfer inhibiting polymer 0.3 0.2

Carbonate 16.0 14.0 24.0 6.0 23.0

Silicate 3.0 0.6 12.5 0.6

Sulfate, Water, Perfume, Colorants balanc balance balance balance balanc e e

*particulate bleach additive composition according to Example III or IV

The above exemplified granular detergent compositions unexpectedly have superior cleaning performance as well as physical properties.

Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

WHAT IS CLAIMED IS:

1. A particulate bleach additive composition characterized by:

(a) from 1% to 90% by weight of carrier particles;

(b) from 1% to 70% by weight of a liquid bleach activator compound having the formula

wherein Ri is a C7-C13 linear or branched chain saturated or unsaturated alkyl group, R2 is a C j-Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C1-C4 linear or branched chain saturated or unsaturated alkyl group; and

(c) from 1% to 75% of a liquid binder; wherein said bleach activator and said liquid activator are coated in and onto the carrier particles.

2. An additive composition according to claim 1 wherein said carrier particles are selected from the group consisting of silicas, aluminosilicates and mixtures thereof.

3. An additive composition according to claim 2 wherein said carrier particles are precipitated silica.

4. An additive composition according to claims 1 -3 wherein said carrier particles have a median particle size in a range from 0.5 microns to 10 microns.

5. An additive composition according to claims 1 -4 the median particle size of said additive composition is in a range of from 700 microns to 800 microns.

6. An additive composition according to dams I -3 wherein R2 is a C \ to C4 linear saturated alkyl group.

7. An additive composition according to claims 1 -6 wherein R 1 is a linear Cg or C9 saturated alkyl group and R2 and R3 are CH3

8. An additive composition according to claims 1-7 wherein the binder is a C_j2-I3 linear alkylbenzene sulfonate surfactant.

9. A particulate bleach additive composition characterized by:

(a) from 1% to 90% by weight of carrier particles;

wherein Rj is a C7-C 13 linear or branched chain saturated or unsaturated alkyl group, R2 is a Ci-Cg linear or branched chain saturated or unsaturated alkyl group and R3 is a C 1-C4 linear or branched chain saturated or unsaturated alkyl group; and

(c) a liquid binder system including

(i) from 0.5% to 15% of C 12-13 linear alkylbenzene sulfonate surfactant,

(ii) from 1% to 25% of polyethylene glycol,

(iii) from 0.5% to 10% of pelargonic acid, and

(iv) from 1% to 25% of palmitic acid; wherein said bleach activator and said liquid activator are coated in and onto die carrier particles.

10. An additive composition according to claim 9 wherein said carrier particles are selected from the group consisting of silicas, aiuminosilicates and mixtures thereof.