USOO9598660B2

(12) United States Patent (10) Patent No.: US 9,598,660 B2 Olson et al. (45) Date of Patent: *Mar. 21, 2017

(54) DETERGENT COMPOSITION INCLUDING A 4,888,123. A 12/1989 Price et al. SACCHARDE OR ALCOHOL 5,114,611 A 5, 1992 Van Kralingen et al. 5,194,172 A * 3/1993 Taneri ...... C11D 9,262 510,139 (71) Applicant: Ecolab USA Inc., St. Paul, MN (US) 5,575,840 A 1 1/1996 Dewacker (72) Inventors: Erik C. Olson, Savage, MN (US); 5,904,735Ai. A 3365, 1999 SEI.Guti tal. Carter M. Silvernail, Burnsville, MN 6,017,864 A 1/2000 Brittain et al. (US) 6,365,568 B1 4/2002 Olson et al. 6,376.440 B1 4/2002 Hennen et al. (73) Assignee: Ecolab USA Inc., St. Paul, MN (US) 6,613,733 B1*ck 9/2003 Barnabas ...... clip: 7,645,731 B1 1, 2010 S1 il et al. (*) Notice: Subject to any disclaimer, the term of this 8,216,989 B2 7/2012 SE I. patent is extended or adjusted under 35 8,263,540 B2 9/2012 Olson et al. U.S.C. 154(b) by 99 days. 8,822.403 B2 * 9/2014 Olson ...... C11D 7/04 134,252 This patent is Subject to a terminal dis- 2002/0022584 A1 2/2002 ASSmann et al. claimer. 2002fOO86809 A1 7/2002 Guo et al. 2003/0203828 A1 10, 2003 Bachmann et al. 2004.0005994 A1 1/2004 Eskuchen et al. (21) Appl. No.: 14/340,127 2007/01790.73 A1 8, 2007 Smith et al. 2008. O188390 A1 8, 2008 Schinkel et al. (22) Filed: Jul. 24, 2014 2009 OO82248 A1 3, 2009 Jones 2009, O156454 A1 6/2009 Schmiedel et al. (65) Prior Publication Data 2009,0186795 A1 7, 2009 Feenstra et al. 2010/O197545 A1 8, 2010 Silvernail et al. US 2014/0336099 A1 Nov. 13, 2014 2010/0298.192 A1 11/2010 Feenstra et al. O O 2011 OO53821 A1 3/2011 Silvernail et al. Related U.S. Application Data 2011 0071065 A1 3f2011 Silvernail et al. 2011/018O112 A1 7, 2011 Silvernail et al. (63) y applian S.G. 8,488, filed on 2012/0053104 A1 3/2012 Olson et al. (60) Provisional application No. 61/434,668, filed on Jan. FOREIGN PATENT DOCUMENTS 20, 2011. EP 1953.217 A1 8, 2008 (51) Int. Cl. EP 1953.217 B1 8/2009 CLID 3/22 (2006.01) WO 9847994 10, 1998 CLID 3/08 (2006.01) CLID 3/10 (2006.01) OTHER PUBLICATIONS CLID 3/37 (2006.01) & 8 CLID (7/06 (2006.01) Peschard, A. et al., “Effect of on the hydration of CLID (7/00 (2006.01) cement paste at early stages' 44 pages, Jan. 30, 2007. BOSB 9/20 (2006.01) k . CLID 704 (2006.01) cited by examiner t 2. 3:08: Primary Examiner — Lorna Douyon CLID 7/26 (2006.015 (74) Attorney, Agent, or Firm — McKee, Voorhees & (52) U.S. Cl. Sease, PLC CPC (2013.01),...... CIIDCIID 3206s 3/221 (2013.01);(2013.01). CIIDCID 3/08704 (57) ABSTRACT (2013.01); CIID 7/14 (2013.01); CIID 7/262 Solid detergent compositions according to the present inven (2013.01); CIID 17/0056 (2013.01) tion include at least one alkali metal silicate, at least one (58) Field of Classification Search polycarboxylic acid, at least one saccharide or Sugar alcohol None and water. Suitable Saccharides include , , See application file for complete search history. , and , and may be present in the composition in a concentration of at least 0.5 wt %. Com (56) References Cited positions according to certain embodiments form stable U.S. PATENT DOCUMENTS Solid block detergent compositions that do not Swell signifi M cantly even when subjected to elevated temperatures. 4,289,643 A 9, 1981 Joubert 4,536,319 A 8/1985 Payne 23 Claims, 6 Drawing Sheets U.S. Patent Mar. 21, 2017 Sheet 1 of 6 US 9,598,660 B2

U.S. Patent US 9,598,660 B2

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U.S. Patent Mar. 21, 2017 Sheet S of 6 US 9,598,660 B2

G(61-) U.S. Patent Mar. 21, 2017 Sheet 6 of 6 US 9,598,660 B2

9(61-) |$$6 US 9,598,660 B2 1. 2 DETERGENT COMPOSITION INCLUDING A FIG. 3 is a line graph illustrating percent Swelling of SACCHARDE OR SUGAR ALCOHOL embodiments of the invention set forth in the Examples. FIG. 4 is a line graph illustrating capsule growth of CROSS-REFERENCE TO RELATED embodiments of the invention set forth in the Examples. APPLICATIONS FIG. 5 is a line graph illustrating percent swelling of embodiments of the invention set forth in the Examples. This is a Continuation Application of U.S. Ser. No. FIG. 6 is a line graph illustrating capsule growth of 13/268,488 filed Oct. 7, 2011, now issued U.S. Pat. No. embodiments of the invention set forth in the Examples. 8.22.403 on Sep. 2, 2014, which application claims the benefit of 35 U.S.C. S 119(e) to U.S. Provisional Patent 10 DETAILED DESCRIPTION Application No. 61/434,668, filed on Jan. 20, 2011, entitled “Detergent Composition including a Saccharide, all of Embodiments of the present invention provide solid, which are incorporated herein by reference in their entirety. dimensionally stable, compositions including at least one alkali metal silicate cleaning agent, water and at least one BACKGROUND 15 saccharide or Sugar alcohol. Such compositions may be particularly useful in cleaning applications where it is The present invention relates generally to the field of solid detergent compositions. In particular, the present invention desired to use a phosphate-free detergent. Such applications relates to Solid detergent compositions containing saccha include, but are not limited to: machine and manual ware rides and/or Sugar alcohols. washing, presoaks, laundry and textile cleaning and destain The advent of Solid block detergent compositions con ing, carpet cleaning and destaining, vehicle cleaning and taining alkali cleaning agents has revolutionized the manner care applications, Surface cleaning and destaining, kitchen in which detergents are dispensed by commercial and insti and bath cleaning and destaining, floor cleaning and destain tutional entities which routinely use large quantities of ing, cleaning in place operations, general purpose cleaning cleaning solution. The solid block compositions are gener 25 and destaining, industrial or household cleaners, and pest ally formed by combining the alkali cleaning agent with one control agents. or more solidification components in a liquid solution. The The solid detergent composition includes an effective Solidification components interact with the alkali cleaning amount of alkali metal silicate sources to enhance cleaning agent and cause the composition to form a solid block with of the desired substrate and improve soil removal perfor minimal if any energy input. 30 mance of the Solid composition. The composition may One challenge that arises when transporting and Subse include the alkali metal silicate in an amount of between quently using such solid block compositions is that Swelling about 0.1% by weight and 80% by weight, more particularly, can occur particularly when the Solid block composition is between about 10% by weight and about 60% by weight, subjected to higher temperature conditions. The result is that and even more particularly, between about 25% by weight the block composition may break apart, damage the pack 35 and about 60% by weight. aging in which it is stored and/or not fit properly into An effective amount of one or more alkali metal silicate dispensing machines. Various materials have been added to Sources may provide a use composition (i.e., an aqueous solid block compositions to control swelling. However, Solution containing the composition) having a pH of at least increased regulation of detergent compositions has created a about 8. When the use composition has a pH of between need to identify compounds that help control swelling while 40 about 8 and about 10, it can be considered mildly alkali, and also having a low impact on the environment. when the pH is greater than about 12, the use composition can be considered caustic. SUMMARY Examples of suitable alkali metal silicates include lithium, Sodium and potassium silicate or metasilicate, as One embodiment is a solid detergent composition includ 45 well as combinations of the foregoing materials. The alkali ing at least one alkali metal silicate, at least one saccharide metal silicate may be used to form the composition without or Sugar alcohol and water. Suitable Saccharides include modification or may be combined with other raw materials mono-, di- and polysaccharides containing 3 or more sac Such as alkali metal hydroxide to form alkali metal meta charide units. Sucrose, fructose, inulin, lactulose, maltose silicate prior to or in the process of making the solid and combinations thereof, may be particularly Suitable. 50 composition. Commercial sodium silicates are available in Another embodiment is a solid detergent composition both powdered and liquid forms. The powdered forms including from about 0.1 wt % to about 70 wt % of at least include both amorphous and crystalline powders in either one alkali metal silicate, from about 0.5 wt % to about 10 hydrated or anhydrous form. The aqueous liquids are avail wt % of at least one saccharide or Sugar alcohol, and from able with viscosities ranging from 0.5 to 600,000 centipoise about 10 wt % to about 70 wt % water. A further embodi 55 at 20° C. Potassium silicates are sold either as a glass or an ment is a method of forming a solid detergent composition aqueous liquid. The synthetic lithium silicates typically are in which at least one alkali metal silicate, at least one generally sold only as liquids. The more common commer saccharide or Sugar alcohol and water are combined to form cially available sodium silicates vary in NaO/SiO ratio a mixture, and a Solid detergent composition is then formed from about 2:1 to about 1:4. from the mixture. 60 The solid forms of alkali metal silicates are generally classified by particle-size range and NaO/SiO, ratio. The BRIEF DESCRIPTION OF THE DRAWINGS aqueous solutions are identified by any combination of density/specific gravity, alkali:silica ratio, and Viscosity. FIG. 1 is a line graph illustrating percent Swelling of Typically, the aqueous solutions are differentiated on the embodiments of the invention set forth in the Examples. 65 basis of specific gravity and NaO/SiO ratio. Concentrated FIG. 2 is a line graph illustrating capsule growth of Solutions of highly alkali sodium silicates are quite sticky or embodiments of the invention set forth in the Examples tacky. US 9,598,660 B2 3 4 Conversely, concentrated Solutions of highly siliceous TABLE 1. Sodium silicate show little tack but are plastic enough to form into balls which show a Surprising elasticity. Commercial Solid Silicates The crystalline products which are readily available on a commercial scale are the anhydrous and hydrated sodium 5 Flow metasilicates- (NaSiO, NaSiO5HO and SiO 9HO) and MO:SiO. (3 %0. 0.% 0.% Softening Pt the hydrated sodium2 - sesquisilicates3: . c2 is - . 12 (NaHSiO Y3 5H2O2 and Name (wt) M-O2 SO 2 HO2 Pt ( C.) ( C.) 3Na2O, SiO, 11HO). The anhydrous sodium sesquisilicate Sodium 1:3.22 23.5 75.7 655 840 and the technically anhydrous orthosilicates are also avail- Silicate 1:200 33.0 66.O 590 760 able but generally mixtures of caustic soda and sodium (anhydrous metasilicate. glasses) The liquid products which are readily available on a Potassium 1:2SO 28.3 70.7 700 905 commercial scale include MO:SiO ratios from about 1:1.5 Silicate to 1:3.8 for sodium silicate and about 1:1.5 to about 1:2.5 for you potassium silicate with a water content from about 45 to glasses) a bout 75 wt.%O based uponp the weight9. of the silicate and the ' Silicates" 1:2.OO1:322 27.019.2 S4O61.8 18.5 water. - (hydrated A listing of commercially available alkali metal silicates amphorous are provided in Tables 1-2 below. The physical properties of powders) various crystalline alkali silicates are provided in Table 3 below. TABLE 2

(MO:SiO2) Baume Viscosity Name (wt) % MO % SiO, at 20° C. Specific Gravity (Poise/20° C.)

Sodium :160 19.7O 31.5 58.3 1.68 7O.OO Silicate :200 18.00 36.0 59.3 1.69 7OOOO (solutions) 1:2.50 10.60 26.5 42.O 1.41 O.6O :288 11.OO 31.7 47.0 1.49 96.O 3.22 8.90 28.7 410 1.39 18O :3.75 6.8O 25.3 35.0 1.32 2.2O Potassium 1:2.50 8.30 20.8 29.8 1.26 O4O Silicate :220 9.OS 19.9 3O.O 1.26 O.O7 (solutions) 1:2.10 12.SO 26.3 40.O 1.38 1O.SO :18O 1040 29.5 47.7 1.49 13.00 Lithium :9.4 2.20 20.7 Silicate :9.6 2.10 20.O 4.OO (solutions) 1:11.8 1.60 18.8 :17.0 1.20 20.O 2.50

TABLE 3 Melting Point Density AH calfwt RI Name Formula (° C.) (g/ml) at 25° RI alpha RI beta gamma Sodium NaSiO, 1118 2.50 –497,800 1.524 — 537 Orthosilicate (2NaOSIO) Sodium NaSi2O7 1122 2.96 –856,300 1.524 — S29 Sesquisilicate (3Na2O2SiO2) Sodium NaSiO75H2O 88 -1,648,000 1. SO2 1.510 1.524 Sesquisilicate (3Na2O2SiO2.5H2O) Pentahydrate Sodium NaSiO, 1089 2,614 -364,700 1490 SOO 1.510 Metasilicate (NaOSiO2) Sodium Na2SiO5H2O 72.2 1.749 -722,100 1447 1454. 1467 Metasilicate (NaOSi-O-5H2O) Pentahydrate Sodium Na2SiO6H2O 70 1.807 -792,600 1488 495 Metasilicate (NaOSiO6H2O) 62.9 146S 1.475 465 hexahydrate Sodium NaSiO3H2O 48.35 1.672 -934,800 147S 1463 465 Metasilicate (NaOSiO8H2O) Octahydrate Sodiuin Na2SiO9H2O 47.85 1.646 -1,005,100 1451 1456 1460 Metasilicate (NaOSiO,9HO) Nanohydrate Sodiuin Na2Si2O5 874 2.964 -576,100 1...SOO 1.510 1.518 US 9,598,660 B2 5 6 The solid composition may include between about 0.1% include a smaller amount of water for Solidification com by weight and about 25% by weight saccharide or Sugar pared with the casting techniques. When preparing the Solid alcohol, more particularly, between about 1.0% by weight detergent composition by casting techniques, water may be and about 15% by weight saccharide or Sugar alcohol, even present in ranges of between about 5% and about 50% by more particularly, between about 1.0% by weight and about weight, particularly between about 10% and about 40% by 10% by weight saccharide or Sugar alcohol, and even more weight, and more particularly between about 20% and about particularly from about 1.0% by weight to about 7.0% by 40% by weight. weight saccharide or Sugar alcohol. The composition may optionally include at least about Suitable saccharides for use with embodiments of the 0.5% by weight of polycarboxylic acid polymer, copolymers present invention include , 10 and/or salts thereof, more particularly, from about 1% by and polysaccharides, and in particular mono-, di- and poly weight to about 25% by weight, even more particularly, from saccharides containing 3 or more saccharide units. Suitable about 3% by weight to about 15% by weight. Examples of saccharides can have a cyclic or non-cyclic structure. Exem Suitable polycarboxylic acid polymer include, but are not plary saccharides include, but are not limited to , limited to: polyacrylic acid polymers, polyacrylic acid poly fructose, lactulose , , , Sucrose, 15 mers modified by a fatty acid end group (“modified poly maltose, , , raffinose, , maltri acrylic acid polymers'), and polymaleic acid polymers. ose, , , , , , , Examples of particularly Suitable polyacrylic acid polymers , , , , , , man and modified polyacrylic acid polymers include those hav nose, , , , , , , ing a molecular weight of between about 1,000 g/mol and Sedohepulose, octuse, nonose, , theose, , about 100,000 g/mol. Examples of more particularly suitable , , inulin, modified inulin, potato , polymaleic acid polymers include those having a molecular modified potato starch, corn starch, modified corn starch, weight of between about 500 g/mol and about 5,000 g/mol. wheat starch, modified wheat starch, rice starch, modified An example of particularly suitable commercially avail rice starch, , modified cellulose, , , able polyacrylic acid polymer includes, but is not limited to, , cyclodextrin, and oligiofructose, 25 Acusol 445N, available from Rohm & Haas LLC, Philadel Sodium carboxymethylcellulose, linear Sulfonated C-(1,4)- phia, Pa. An example of particularly suitable commercially linked D-glucose polymers, Y-cyclodextrin and the like. available modified polyacrylic acid polymer includes, but is Sugar alcohols may also be suitable. Examples of particu not limited to, Alcosperse 325, available from Alco Chemi larly Suitable Saccharide based include, but are not cal, Chattanooga, Tenn. Examples of particularly Suitable limited to Sucrose, fructose, inulin, lactulose, maltose and 30 commercially available polymaleic acid polymers include, combinations thereof but are not limited to: Belclene 200, available from Hough Examples of suitable inulin saccharides include, but are ton Chemical Corporation, Boston, Mass. and Aquatreat not limited to, naturally-occurring and derivatized . AR-801, available from Alco Chemical, Chattanooga, Tenn. Derivatized inulins are modified to be further substituted at In one embodiment, at least two polycarboxylic acid a varying number of the available hydroxyls, with alkyl, 35 polymers are used. For example, the combination of at least alkoxy, carboxy, and carboxyalkyl moieties, for example. one polyacrylic acid and at least one polymaleic acid may be Examples of particularly suitable commercially available used to provide the composition with suitable solidification carboxymethyl inulin-based polymers include, but are not properties. The polycarboxylic acid combinations may fur limited to: Dequest PB 11615, Dequest PB 11620 and ther function as a corrosion inhibitor. Dequest PB 11625, available from Solutia, Inc., St. Louis, 40 The Solid detergent composition may be phosphorus-free Mo. DEQUEST PB 11625 is a 20% solution of carboxym and/or nitrilotriacetic acid (NTA)-free to make the solid ethyl inulin, sodium salt, having a MW-2000. detergent composition more environmentally beneficial. As discussed above, Sugar alcohols may also be Suitable. Phosphorus-free means a composition having less than Examples of Suitable Sugar alcohols include, but are not approximately 0.5 wt %, more particularly, less than limited to, glycol, glycerol, erythritol, threitol, arabitol, 45 approximately 0.1 wt %, and even more particularly less xylitol, ribitol, mannitol, sorbitol, dulcitol, iditol, isomalt, than approximately 0.01 wt % phosphorous based on the malitol, polyglycitol, lactitol, and other polyols. Examples total weight of the composition. NTA-free means a compo of particularly Suitable Sugar alcohols include but are not sition having less than approximately 0.5 wt %, less than limited to sorbitol. approximately 0.1 wt %, and particularly less than approxi Water may be independently added to the composition or 50 mately 0.01 wt % NTA based on the total weight of the may be provided in the composition as a result of its composition. When the composition is NTA-free, it is also presence in an aqueous material that is added to the deter compatible with chlorine, which functions as an anti-rede gent composition. For example, materials added to the position and stain-removal agent. detergent composition may include water or may be pre If the solid detergent composition swells after solidifica pared in an aqueous premix. Typically, water is introduced 55 tion, various problems may occur, including but not limited into the composition to provide a desired viscosity for to: decreased density, integrity, appearance, and inability to processing prior to Solidification and to provide a desired dispense or package the Solid product. Generally, a solid rate of solidification. The water may also be present as a product is considered to have dimensional stability if the processing aid and may be removed or become water of Solid product has a growth exponent (i.e., percent Swelling) hydration. The water may also be provided as deionized 60 of less than about 3% and particularly less than about 2%. water or as softened water. Growth exponent refers to the percent growth of a product The amount of water in the resulting Solid detergent over a period of time after solidification under normal composition will depend on whether the solid detergent transport/storage conditions. Because normal transport/stor composition is processed through forming techniques or age conditions for detergent products may result in the Solid casting (Solidification occurring within a container) tech 65 detergent composition being Subjected to an elevated tem niques. In general, when the components are processed by perature, the growth exponent may be determined by mea forming techniques, the Solid detergent composition may Suring one or more dimensions of the Solid product prior to US 9,598,660 B2 7 and after heating to between 100°F. and 120° F. for several TABLE 4 hours, days or even weeks. The measured dimension First Second depends on the shape of the Solid detergent composition. For Exemplary Exemplary tablet shaped compositions, both diameter and height are Material Wt 9% Range Wt % Range generally measured. For capsule shaped compositions, only Water 10-70 1O-30 diameter is generally measured. Sodium Metasilicate O. 1-70 25-50 Embodiments of the present invention including a sac polycarboxylic acid polymer(s) 1-15 5-15 charide or Sugar alcohol may have a growth exponent that is Sodium Carbonate 15-40 15-40 less than the growth exponent of the same composition Surfactant O.OS-20 O. 1-5 without a saccharide or Sugar alcohol. More particularly, of 10 Saccharide or Sugar alcohol O. 1-25 O. 1-7 the present invention including a saccharide or Sugar alcohol may have a growth exponent that is less than about 3%, more Surfactants particularly, less than about 2% when subjected to elevated The Solid detergent composition can include at least one temperatures of at least about 100° F., more particularly, cleaning agent comprising a surfactant or Surfactant system. about 120° F. More particularly, the growth exponent may 15 A variety of Surfactants can be used in a Solid detergent remain below 2% even after heating at 120° F. for at least composition, including, but not limited to: anionic, non about three weeks. ionic, cationic, and Zwitterionic Surfactants. Surfactants are Additional Functional Materials an optional component of the solid detergent composition The components of the detergent composition can be and can be excluded from the concentrate. Exemplary Sur combined with various functional components. In some factants that can be used are commercially available from a embodiments, the alkali metal silicate, Saccharide or Sugar number of Sources. For a discussion of Surfactants, see alcohol and water make up a large amount, or even Sub Kirk-Othmer, Encyclopedia of Chemical Technology. Third stantially all of the total weight of the detergent composition, Edition, volume 8, pages 900-912. When the solid detergent for example, in embodiments having few or no additional 25 composition includes a Surfactant as a cleaning agent, the functional materials disposed therein. In these embodiments, cleaning agent is provided in an amount effective to provide the component concentration ranges provided above for the a desired level of cleaning. The Solid detergent composition, detergent are representative of the ranges of those same when provided as a concentrate, can include the Surfactant components in the detergent composition. In other embodi cleaning agent in a range of about 0.05% to about 20% by ments, the detergent composition consists essentially of the 30 weight, about 0.5% to about 15% by weight, about 1% to alkali metal silicate, at least one saccharide or Sugar alcohol, about 15% by weight, about 1.5% to about 10% by weight, water, at least one polycarboxylic acid, optionally sodium and about 2% to about 8% by weight. Additional exemplary carbonate, optionally at least one secondary alkali source ranges of Surfactant in a concentrate include about 0.5% to and optionally at least one Surfactant. about 8% by weight, and about 1% to about 5% by weight. The functional materials provide desired properties and 35 Examples of anionic surfactants useful in the solid deter functionalities to the solid detergent composition. For the gent composition include, but are not limited to: carboxy purpose of this application, the term “functional materials’ lates Such as alkylcarboxylates and polyalkoxycarboxylates, includes a material that when dispersed or dissolved in a use alcohol ethoxylate carboxylates, nonylphenol ethoxylate and/or concentrate solution, such as an aqueous solution, carboxylates; Sulfonates such as alkylsulfonates, alkylben provides a beneficial property in a particular use. Some 40 Zenesulfonates, alkylarylsulfonates, Sulfonated fatty acid particular examples of functional materials are discussed in esters; Sulfates Such as Sulfated alcohols, Sulfated alcohol more detail below, although the particular materials dis ethoxylates, Sulfated alkylphenols, alkylsulfates, Sulfo Succi cussed are given by way of example only, and that a broad nates, and alkylether Sulfates. Exemplary anionic Surfactants variety of other functional materials may be used. Moreover, include, but are not limited to: sodium alkylarylsulfonate, the components discussed above may be multi-functional 45 alpha-olefinSulfonate, and fatty alcohol Sulfates. and may also provide several of the functional benefits Examples of nonionic Surfactants useful in the Solid discussed below. detergent composition include, but are not limited to, those Secondary Alkali Source having a polyalkylene oxide polymer as a portion of the The solid detergent composition can include one or more Surfactant molecule. Such nonionic Surfactants include, but secondary alkali sources. Examples of Suitable secondary 50 are not limited to: chlorine-, benzyl-, methyl-, ethyl-, pro alkali sources of the solid detergent composition include, but pyl-, butyl- and other like alkyl-capped polyethylene glycol are not limited to alkali metal carbonates and alkali metal ethers of fatty alcohols; polyalkylene oxide free nonionics hydroxides. Exemplary alkali metal carbonates that can be Such as alkyl polyglycosides; Sorbitan and Sucrose esters and used include, but are not limited to: Sodium or potassium their ethoxylates; alkoxylated amines such as alkoxylated carbonate, bicarbonate, sesquicarbonate, and mixtures 55 ethylene diamine; alcohol alkoxylates such as alcohol thereof. Exemplary alkali metal hydroxides that can be used ethoxylate propoxylates, alcohol propoxylates, alcohol include, but are not limited to: Sodium or potassium hydrox propoxylate ethoxylate propoxylates, alcohol ethoxylate ide. The alkali metal hydroxide may be added to the com butoxylates; nonylphenol ethoxylate, polyoxyethylene gly position in any form known in the art, including as Solid col ether, carboxylic acid esters such as glycerol esters, beads, dissolved in an aqueous solution, or a combination 60 polyoxyethylene esters, ethoxylated and glycol esters of thereof. In some embodiments, the detergent composition fatty acids; carboxylic amides such as diethanolamine con does not include a secondary detergent source Such as densates, monoalkanolamine condensates, polyoxyethylene Sodium carbonate. If included, the secondary alkali source, fatty acid amides; and polyalkylene oxide block copolymers. for example sodium carbonate, may be present in concen An example of a commercially available ethylene oxide/ tration of from 15-40 wt %. An exemplary detergent com 65 propylene oxide block copolymer includes, but is not limited position including carbonate may have the following com to, PLURONICR), available from BASF Corporation, Flo ponent and component concentrations: rham Park, N.J. An example of a commercially available US 9,598,660 B2 10 silicone surfactant includes, but is not limited to, ABIL(R) detergent composition by fixing the free water present in the B8852, available from Goldschmidt Chemical Corporation, composition as water of hydration. Hopewell, Va. Examples of phosphonates included, but are not limited Examples of cationic Surfactants that can be used in the to: 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), Solid detergent composition include, but are not limited to: 1-hydroxyethane-1, 1-diphosphonic acid, CHC(OH)PO amines such as primary, secondary and tertiary monoamines (OH); aminotri (methylenephosphonic acid), NICHPO with Cs alkyl or alkenyl chains, ethoxylated alkylamines, (OH), aminotri (methylenephosphonate), sodium salt alkoxylates of ethylenediamine, imidazoles such as a 1-(2- (ATMP), NICHPO(ONa); 2-hydroxyethyliminobis hydroxyethyl)-2-imidazoline, a 2-alkyl-1-(2-hydroxyethyl)- (methylenephosphonic acid), HOCHCHNICHPO 10 (OH)2. diethylenetriaminepenta(methylenephosphonic 2-imidazoline, and the like; and quaternary ammonium salts, acid), (HO), POCHNICHCHNICHPO(OH); dieth as for example, alkylquaternary ammonium chloride Surfac ylenetriaminepenta(methylenephosphonate), sodium salt tants such as n-alkyl(C-Cs)dimethylbenzyl ammonium (DTPMP), CHs N,Na,C), sPs (x-7); hexamethylenedi chloride, n-tetradecyldimethylbenzylammonium chloride amine(tetramethylenephosphonate), potassium salt, monohydrate, and a naphthylene-substituted quaternary 15 CoHas N.K.O.P., (X-6); bis(hexamethylene)triamine ammonium chloride such as dimethyl-1-naphthylmethylam (pentamethylenephosphonic acid), (HO)POCHN (CH), monium chloride. The cationic Surfactant can be used to NICH2 poorlla; and phosphorus acid, HPOs. A pre provide Sanitizing properties. ferred phosphonate combination is ATMP and DTPMP. A Examples of Zwitterionic Surfactants that can be used in neutralized or alkali phosphonate, or a combination of the the solid detergent composition include, but are not limited phosphonate with an alkali source prior to being added into to: betaines, imidazolines, and propionates. the mixture such that there is little or no heat or gas Because the Solid detergent composition is intended to be generated by a neutralization reaction when the phosphonate used in an automatic dishwashing or warewashing machine, is added is preferred. In one embodiment, however, the the Surfactants selected, if any Surfactant is used, can be detergent composition if free of phosphorous. those that provide an acceptable level of foaming when used 25 Useful aminocarboxylic acid materials containing little or inside a dishwashing or warewashing machine. Solid deter no NTA include, but are not limited to: N-hydroxyethylam gent compositions for use in automatic dishwashing or inodiacetic acid, ethylenediaminetetraacetic acid (EDTA), warewashing machines are generally considered to be low hydroxyethylenediaminetetraacetic acid, diethylenetri foaming compositions. Low foaming Surfactants that pro aminepentaacetic acid, N-hydroxyethyl-ethylenediaminetri vide the desired level of detersive activity are advantageous 30 acetic acid (HEDTA), diethylenetriaminepentaacetic acid in an environment such as a dishwashing machine where the (DTPA), methylglycinediacetic acid (MGDA), glutamic presence of large amounts of foaming can be problematic. In acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic addition to selecting low foaming Surfactants, defoaming acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), agents can also be utilized to reduce the generation of foam. iminodisuccinic acid (IDS), 3-hydroxy-2-2'-iminodisuccinic Accordingly, Surfactants that are considered low foaming 35 acid (HIDS) and other similar acids or salts thereof having Surfactants can be used. In addition, other Surfactants can be an amino group with a carboxylic acid Substituent. In one used in conjunction with a defoaming agent to control the embodiment, however, the composition if free of aminocar level of foaming. boxylates. Builders or Water Conditioners Water conditioning polymers can be used as non-phos The solid detergent composition can include one or more 40 phorus containing builders. Exemplary water conditioning building agents, also called chelating or sequestering agents polymers include, but are not limited to: polycarboxylates. (e.g., builders), including, but not limited to: condensed Exemplary polycarboxylates that can be used as builders phosphates, alkali metal carbonates, phosphonates, amin and/or water conditioning polymers include, but are not ocarboxylic acids, and/or polyacrylates. In general, a chelat limited to: those having pendant carboxylate (—CO) ing agent is a molecule capable of coordinating (i.e., bind 45 groups such as polyacrylic acid, maleic acid, maleic/olefin ing) the metal ions commonly found in natural water to copolymer, Sulfonated copolymer or terpolymer, acrylic/ prevent the metal ions from interfering with the action of the maleic copolymer, polymethacrylic acid, acrylic acid-meth other detersive ingredients of a cleaning composition. Pref acrylic acid copolymers, hydrolyzed polyacrylamide, hydro erable levels of addition for builders that can also be lyzed polymethacrylamide, hydrolyzed polyamide chelating or sequestering agents are between about 0.1% to 50 methacrylamide copolymers, hydrolyzed polyacrylonitrile, about 70% by weight, about 1% to about 60% by weight, or hydrolyzed polymethacrylonitrile, and hydrolyzed acryloni about 1.5% to about 50% by weight. If the solid detergent is trile-methacrylonitrile copolymers. Other suitable water provided as a concentrate, the concentrate can include conditioning polymers include starch, Sugar or polyols com between approximately 1% to approximately 60% by prising carboxylic acid or ester functional groups. Exem weight, between approximately 3% to approximately 50% 55 plary carboxylic acids include but are not limited to maleic, by weight, and between approximately 6% to approximately acrylic, methacrylic and itaconic acid or salts thereof. Exem 45% by weight of the builders. Additional ranges of the plary ester functional groups include aryl, cyclic, aromatic builders include between approximately 3% to approxi and C-Co linear, branched or Substituted esters. For a mately 20% by weight, between approximately 6% to further discussion of chelating agents/sequestrants, see Kirk approximately 15% by weight, between approximately 25% 60 Othmer, Encyclopedia of Chemical Technology. Third Edi to approximately 50% by weight, and between approxi tion, volume 5, pages 339-366 and volume 23, pages 319 mately 35% to approximately 45% by weight. 320, the disclosure of which is incorporated by reference Examples of condensed phosphates include, but are not herein. These materials may also be used at Substoichiomet limited to: Sodium and potassium orthophosphate, sodium ric levels to function as crystal modifiers and potassium pyrophosphate, sodium tripolyphosphate, and 65 Hardening Agents Sodium hexametaphosphate. A condensed phosphate may The solid detergent compositions can also include a also assist, to a limited extent, in Solidification of the Solid hardening agent in addition to, or in the form of the builder. US 9,598,660 B2 11 12 A hardening agent is a compound or system of compounds, compounds include, but are not limited to: PEG 4000, PEG organic or inorganic, which significantly contributes to the 1450, and PEG 8000 among others, with PEG 4000 and PEG uniform solidification of the composition. Preferably, the 8000 being most preferred. An example of a commercially hardening agents are compatible with the cleaning agent and available solid polyethylene glycol includes, but is not other active ingredients of the composition and are capable 5 limited to: CARBOWAX, available from Union Carbide of providing an effective amount of hardness and/or aqueous Corporation, Houston, Tex. solubility to the processed composition. The hardening Preferred inorganic hardening agents are hydratable inor agents should also be capable of forming a homogeneous ganic salts, including, but not limited to: Sulfates and bicar matrix with the cleaning agent and other ingredients when bonates. The inorganic hardening agents are present at mixed and solidified to provide a uniform dissolution of the 10 concentrations of up to approximately 50% by weight, cleaning agent from the Solid detergent composition during particularly approximately 5% to approximately 25% by SC. weight, and more particularly approximately 5% to approxi The amount of hardening agent included in the solid mately 15% by weight. In one embodiment, however, the detergent composition will vary according to factors includ solid composition if free of sulfates and carbonates includ ing, but not limited to: the type of Solid detergent compo- 15 ing Soda ash. sition being prepared, the ingredients of the Solid detergent Urea particles can also be employed as hardeners in the composition, the intended use of the composition, the quan solid detergent compositions. The solidification rate of the tity of dispensing solution applied to the Solid composition compositions will vary, at least in part, to factors including, over time during use, the temperature of the dispensing but not limited to: the amount, the particle size, and the Solution, the hardness of the dispensing Solution, the physi- 20 shape of the urea added to the composition. For example, a cal size of the Solid detergent composition, the concentration particulate form of urea can be combined with a cleaning of the other ingredients, and the concentration of the clean agent and other ingredients, and preferably a minor but ing agent in the composition. It is preferred that the amount effective amount of water. The amount and particle size of of the hardening agent included in the solid detergent the urea is effective to combine with the cleaning agent and composition is effective to combine with the cleaning agent 25 other ingredients to form a homogeneous mixture without and other ingredients of the composition to form a homo the application of heat from an external Source to melt the geneous mixture under continuous mixing conditions and a urea and other ingredients to a molten stage. It is preferred temperature at or below the melting temperature of the that the amount of urea included in the solid detergent hardening agent. composition is effective to provide a desired hardness and It is also preferred that the hardening agent form a matrix 30 desired rate of solubility of the composition when placed in with the cleaning agent and other ingredients which will an aqueous medium to achieve a desired rate of dispensing harden to a solid form under ambient temperatures of the cleaning agent from the solidified composition during approximately 30° C. to approximately 50° C., particularly use. In some embodiments, the composition includes approximately 35° C. to approximately 45° C., after mixing between approximately 5% to approximately 90% by weight ceases and the mixture is dispensed from the mixing system, 35 urea, particularly between approximately 8% and approxi within approximately 1 minute to approximately 3 hours, mately 40% by weight urea, and more particularly between particularly approximately 2 minutes to approximately 2 approximately 10% and approximately 30% by weight urea. hours, and particularly approximately 5 minutes to approxi The urea may be in the form of prilled beads or powder. mately 1 hour. A minimal amount of heat from an external Prilled urea is generally available from commercial sources Source may be applied to the mixture to facilitate processing 40 as a mixture of particle sizes ranging from about 8-15 U.S. of the mixture. It is preferred that the amount of the mesh, as for example, from Arcadian Sohio Company, hardening agent included in the Solid detergent composition Nitrogen Chemicals Division. A prilled form of urea is is effective to provide a desired hardness and desired rate of preferably milled to reduce the particle size to about 50 U.S. controlled solubility of the processed composition when mesh to about 125 U.S. mesh, particularly about 75-100 U.S. placed in an aqueous medium to achieve a desired rate of 45 mesh, preferably using a wet mill such as a single or dispensing the cleaning agent from the solidified composi twin-screw extruder, a Teledyne mixer, a Ross emulsifier, tion during use. and the like. The hardening agent may be an organic or an inorganic Bleaching Agents hardening agent. A preferred organic hardening agent is a Bleaching agents suitable for use in the solid detergent polyethylene glycol (PEG) compound. The solidification 50 composition for lightening or whitening a Substrate include rate of Solid detergent compositions comprising a polyeth bleaching compounds capable of liberating an active halo ylene glycol hardening agent will vary, at least in part, gen species, such as Cl, Br, —OCl and/or —OBr, under according to the amount and the molecular weight of the conditions typically encountered during the cleansing pro polyethylene glycol added to the composition. Examples of cess. Suitable bleaching agents for use in the Solid detergent suitable polyethylene glycols include, but are not limited to: 55 compositions include, but are not limited to: chlorine-con Solid polyethylene glycols of the general formula taining compounds such as chlorines, hypochlorites, or H(OCH2CH), OH, where n is greater than 15, particularly chloramines. Exemplary halogen-releasing compounds approximately 30 to approximately 1700. Typically, the include, but are not limited to: the alkali metal dichloroiso polyethylene glycol is a solid in the form of a free-flowing cyanurates, chlorinated trisodium phosphate, the alkali powder or flakes, having a molecular weight of approxi- 60 metal hypochlorites, monochloramine, and dichloramine. mately 1,000 to approximately 100,000, particularly having Encapsulated chlorine sources may also be used to enhance a molecular weight of at least approximately 1,450 to the stability of the chlorine source in the composition (see, approximately 20,000, more particularly between approxi for example, U.S. Pat. Nos. 4,618.914 and 4,830,773, the mately 1,450 to approximately 8,000. The polyethylene disclosure of which is incorporated by reference herein). A glycol is present at a concentration of from approximately 65 bleaching agent may also be a peroxygen or active oxygen 1% to 75% by weight and particularly approximately 3% to Source Such as hydrogen peroxide, perborates, sodium car approximately 15% by weight. Suitable polyethylene glycol bonate peroxyhydrate, potassium permonosulfate, and US 9,598,660 B2 13 14 sodium perborate mono and tetrahydrate, with and without approximately 0.5% and approximately 15% by weight, and activators such as tetraacetylethylene diamine. When the between approximately 2% and approximately 10% by concentrate includes a bleaching agent, it can be included in weight. an amount of between approximately 0.1% and approxi Dispersants mately 60% by weight, between approximately 1% and 5 The solid detergent composition may also include disper approximately 20% by weight, between approximately 3% sants. Examples of Suitable dispersants that can be used in and approximately 8% by weight, and between approxi the Solid detergent composition include, but are not limited mately 3% and approximately 6% by weight. to: maleic acid?olefin copolymers, polyacrylic acid, and Fillers mixtures thereof. The concentrate need not include a dis 10 persant, but when a dispersant is included it can be included The Solid detergent composition can include an effective in an amount that provides the desired dispersant properties. amount of detergent fillers which do not perform as a Exemplary ranges of the dispersant in the concentrate can be cleaning agent perse, but cooperates with the cleaning agent up to approximately 20% by weight, between approximately to enhance the overall cleaning capacity of the composition. 0.5% and approximately 15% by weight, and between Examples of detergent fillers suitable for use in the present 15 approximately 2% and approximately 9% by weight. cleaning compositions include, but are not limited to: Enzymes sodium sulfate and sodium chloride. When the concentrate Enzymes that can be included in the solid detergent includes a detergent filler, it can be included in an amount up composition include those enzymes that aid in the removal to approximately 50% by weight, between approximately of starch and/or protein stains. Exemplary types of enzymes 1% and approximately 30% by weight, or between approxi include, but are not limited to: proteases, alpha-amylases, mately 1.5% and approximately 25% by weight. and mixtures thereof. Exemplary proteases that can be used Defoaming Agents include, but are not limited to: those derived from Bacillus A defoaming agent for reducing the stability of foam may licheniformix, Bacillus lenus, Bacillus alcalophilus, and also be included in the warewashing composition. Examples Bacillus amyloliquefacins. Exemplary alpha-amylases of defoaming agents include, but are not limited to: ethylene 25 include Bacillus subtilis, Bacillus amyloliquefaceins and oxide?propylene block copolymers such as those available Bacillus licheniformis. The concentrate need not include an under the name Pluronic N-3; silicone compounds such as enzyme, but when the concentrate includes an enzyme, it silica dispersed in polydimethylsiloxane, polydimethylsilox can be included in an amount that provides the desired ane, and functionalized polydimethylsiloxane Such as those enzymatic activity when the Solid detergent composition is available under the name Abil B9952; fatty amides, hydro 30 provided as a use composition. Exemplary ranges of the carbon waxes, fatty acids, fatty esters, fatty alcohols, fatty enzyme in the concentrate include up to approximately 15% acid soaps, ethoxylates, mineral oils, polyethylene glycol by weight, between approximately 0.5% to approximately esters, and alkyl phosphate esters such as monostearyl 10% by weight, and between approximately 1% to approxi phosphate. A discussion of defoaming agents may be found, mately 5% by weight. for example, in U.S. Pat. No. 3,048.548 to Martin et al., U.S. 35 Glass and Metal Corrosion Inhibitors Pat. No. 3,334,147 to Brunelle et al., and U.S. Pat. No. The Solid detergent composition can include a metal 3,442,242 to Rue et al., the disclosures of which are incor corrosion inhibitor in an amount up to approximately 50% porated herein by reference. When the concentrate includes by weight, between approximately 1% and approximately a defoaming agent, the defoaming agent can be provided in 40% by weight, or between approximately 3% and approxi an amount of between approximately 0.0001% and approxi 40 mately 30% by weight. The corrosion inhibitor is included mately 10% by weight, between approximately 0.001% and in the Solid detergent composition in an amount Sufficient to approximately 5% by weight, or between approximately provide a use solution that exhibits a rate of corrosion and/or 0.01% and approximately 1.0% by weight. etching of glass that is less than the rate of corrosion and/or Anti-Redeposition Agents etching of glass for an otherwise identical use solution The Solid detergent composition can include an anti 45 except for the absence of the corrosion inhibitor. It is redeposition agent for facilitating Sustained Suspension of expected that the use solution will include at least approxi soils in a cleaning Solution and preventing the removed soils mately 6 parts per million (ppm) of the corrosion inhibitor from being redeposited onto the Substrate being cleaned. to provide desired corrosion inhibition properties. It is Examples of Suitable anti-redeposition agents include, but expected that larger amounts of corrosion inhibitor can be are not limited to: polyacrylates, styrene maleic anhydride 50 used in the use solution without deleterious effects. It is copolymers, cellulosic derivatives such as hydroxyethyl expected that at a certain point, the additive effect of cellulose, hydroxypropyl cellulose and carboxymethyl cel increased corrosion and/or etching resistance with increas lulose. When the concentrate includes an anti-redeposition ing corrosion inhibitor concentration will be lost, and addi agent, the anti-redeposition agent can be included in an tional corrosion inhibitor will simply increase the cost of amount of between approximately 0.5% and approximately 55 using the solid detergent composition. The use solution can 10% by weight, and between approximately 1% and include between approximately 6 ppm and approximately approximately 5% by weight. 300 ppm of the corrosion inhibitor, and between approxi Stabilizing Agents mately 20 ppm and approximately 200 ppm of the corrosion The Solid detergent composition may also include Stabi inhibitor. Examples of suitable corrosion inhibitors include, lizing agents. Examples of Suitable stabilizing agents 60 but are not limited to: a combination of a source of alumi include, but are not limited to: borate, calcium/magnesium num ion and a source of Zinc ion, as well as an alkali metal ions, propylene glycol, and mixtures thereof. The concen silicate or hydrate thereof. trate need not include a stabilizing agent, but when the The corrosion inhibitor can refer to the combination of a concentrate includes a stabilizing agent, it can be included in Source of aluminum ion and a source of Zinc ion. The source an amount that provides the desired level of stability of the 65 of aluminum ion and the Source of Zinc ion provide alumi concentrate. Exemplary ranges of the stabilizing agent num ion and Zinc ion, respectively, when the Solid detergent include up to approximately 20% by weight, between composition is provided in the form of a use solution. The US 9,598,660 B2 15 16 amount of the corrosion inhibitor is calculated based upon compositions; increasing the particle size of liquid use the combined amount of the source of aluminum ion and the Solutions when dispensed through a spray nozzle; providing Source of Zinc ion. Anything that provides an aluminum ion the use solutions with vertical cling to Surfaces; providing in a use solution can be referred to as a source of aluminum particle Suspension within the use Solutions; or reducing the ion, and anything that provides a Zinc ion when provided in evaporation rate of the use Solutions. a use Solution can be referred to as a source of Zinc ion. It The rheology modifier may provide a use composition is not necessary for the source of aluminum ion and/or the that is pseudoplastic, in other words the use composition or Source of Zinc ion to react to form the aluminum ion and/or material when left undisturbed (in a shear mode), retains a the Zinc ion. Aluminum ions can be considered a source of high viscosity. However, when sheared, the viscosity of the aluminum ion, and Zinc ions can be considered a source of 10 material is substantially but reversibly reduced. After the Zinc ion. The Source of aluminum ion and the Source of Zinc shear action is removed, the Viscosity returns. These prop ion can be provided as organic salts, inorganic salts, and erties permit the application of the material through a spray mixtures thereof. Exemplary sources of aluminum ion head. When sprayed through a nozzle, the material under include, but are not limited to: aluminum salts such as goes shear as it is drawn up a feed tube into a spray head Sodium aluminate, aluminum bromide, aluminum chlorate, 15 under the influence of pressure and is sheared by the action aluminum chloride, aluminum iodide, aluminum nitrate, of a pump in a pump action sprayer. In either case, the aluminum Sulfate, aluminum acetate, aluminum formate, Viscosity can drop to a point Such that Substantial quantities aluminum tartrate, aluminum lactate, aluminum oleate, alu of the material can be applied using the spray devices used minum bromate, aluminum borate, aluminum potassium to apply the material to a soiled surface. However, once the Sulfate, aluminum Zinc sulfate, and aluminum phosphate. material comes to rest on a soiled Surface, the materials can Exemplary Sources of Zinc ion include, but are not limited regain high viscosity to ensure that the material remains in to: Zinc salts such as Zinc chloride, Zinc sulfate, Zinc nitrate, place on the soil. Preferably, the material can be applied to Zinc iodide, Zinc thiocyanate, Zinc fluorosilicate, Zinc a Surface resulting in a Substantial coating of the material dichromate, Zinc chlorate, Sodium Zincate, Zinc gluconate, that provides the cleaning components in Sufficient concen Zinc acetate, Zinc benzoate, Zinc citrate, Zinc lactate, Zinc 25 tration to result in lifting and removal of the hardened or formate, Zinc bromate, Zinc bromide, Zinc fluoride, Zinc baked-on soil. While in contact with the soil on vertical or fluorosilicate, and Zinc Salicylate. inclined Surfaces, the thickeners in conjunction with the The applicants discovered that by controlling the ratio of other components of the cleaner minimize dripping, sagging, the aluminum ion to the Zinc ion in the use solution, it is slumping or other movement of the material under the possible to provide reduced corrosion and/or etching of 30 effects of gravity. The material should be formulated such glassware and ceramics compared with the use of either that the viscosity of the material is adequate to maintain component alone. That is, the combination of the aluminum contact between substantial quantities of the film of the ion and the Zinc ion can provide a synergy in the reduction material with the soil for at least a minute, particularly five of corrosion and/or etching. The ratio of the source of minutes or more. aluminum ion to the Source of Zinc ion can be controlled to 35 Examples of suitable thickeners or rheology modifiers are provide a synergistic effect. In general, the weight ratio of polymeric thickeners including, but not limited to: polymers aluminum ion to Zinc ion in the use Solution can be between or natural polymers or gums derived from plant or animal at least approximately 6:1, can be less than approximately Sources. Such materials may be polysaccharides such as 1:20, and can be between approximately 2:1 and approxi large molecules having Substantial thicken mately 1:15. 40 ing capacity. Thickeners or rheology modifiers also include Fragrances and Dyes clays. Various dyes, odorants including perfumes, and other A substantially soluble polymeric thickener can be used to aesthetic enhancing agents can also be included in the provide increased viscosity or increased conductivity to the composition. Suitable dyes that may be included to alter the use compositions. Examples of polymeric thickeners for the appearance of the composition, include, but are not limited 45 aqueous compositions of the invention include, but are not to: Direct Blue 86, available from Mac Dye-Chem Indus limited to: carboxylated vinyl polymers such as polyacrylic tries, Ahmedabad, India; Fastusol Blue, available from acids and Sodium salts thereof, ethoxylated cellulose, poly Mobay Chemical Corporation, Pittsburgh, Pa.; Acid Orange acrylamide thickeners, cross-linked, Xanthan compositions, 7, available from American Cyanamid Company, Wayne, Sodium alginate and algin products, hydroxypropyl cellu N.J.; Basic Violet 10 and Sandolan Blue/Acid Blue 182, 50 lose, hydroxyethyl cellulose, and other similar aqueous available from Sandoz, Princeton, N.J.; Acid Yellow 23, thickeners that have some Substantial proportion of water available from Chemos GmbH, Regenstauf, Germany; Acid solubility. Examples of suitable commercially available Yellow 17, available from Sigma Chemical, St. Louis, Mo.; thickeners include, but are not limited to: Acusol, available Sap Green and Metanil Yellow, available from Keyston from Rohm & Haas Company, Philadelphia, Pa.; and Car Analine and Chemical, Chicago, Ill., Acid Blue 9, available 55 bopol, available from B.F. Goodrich, Charlotte, N.C. from Emerald Hilton Davis, LLC, Cincinnati, Ohio; Hisol Examples of suitable polymeric thickeners include, but Fast Red and Fluorescein, available from Capitol Color and not limited to: polysaccharides. An example of a Suitable Chemical Company, Newark, N.J.; and Acid Green 25, Ciba commercially available polysaccharide includes, but is not Specialty Chemicals Corporation, Greenboro, N.C. limited to, Diutan, available from Kelco Division of Merck, Fragrances or perfumes that may be included in the 60 San Diego, Calif. Thickeners for use in the solid detergent compositions include, but are not limited to: terpenoids Such compositions further include polyvinyl alcohol thickeners, as citronellol, aldehydes such as amyl cinnamaldehyde, a such as, fully hydrolyzed (greater than 98.5 mol acetate jasmine Such as C1S-jasmine or jasmal, and Vanillin. replaced with the —OH function). Thickeners An example of a particularly suitable polysaccharide The Solid detergent compositions can include a rheology 65 includes, but is not limited to, Xanthans. Such Xanthan modifier or a thickener. The rheology modifier may provide polymers are preferred due to their high water solubility, and the following functions: increasing the Viscosity of the great thickening power. Xanthan is an extracellular polysac US 9,598,660 B2 17 18 charide of Xanthomonas campestras. Xanthan may be made other shaping means. The product is then packaged. In an by fermentation based on corn Sugar or other corn Sweetener exemplary embodiment, the formed composition begins to by-products. Xanthan comprises a poly beta-(1-4)-D-Glu harden to a solid form in between approximately 1 minute copyranosyl backbone chain, similar to that found in cellu and approximately 3 hours. Particularly, the formed com lose. Aqueous dispersions of and its deriva position begins to harden to a solid form in between approxi tives exhibit novel and remarkable rheological properties. mately 1 minute and approximately 2 hours. More particu Low concentrations of the gum have relatively high viscosi larly, the formed composition begins to harden to a solid ties which permit it to be used economically. Xanthan gum form in between approximately 1 minute and approximately Solutions exhibit high pseudo plasticity, i.e. over a wide 20 minutes. range of concentrations, rapid shear thinning occurs that is 10 In a casting process, the liquid and Solid components are generally understood to be instantaneously reversible. Non introduced into the final mixing system and are continuously sheared materials have viscosities that appear to be inde mixed until the components form a Substantially homoge pendent of the pH and independent of temperature over wide neous liquid mixture in which the components are distrib ranges. Preferred Xanthan materials include crosslinked Xan uted throughout its mass. In an exemplary embodiment, the than materials. Xanthan polymers can be crosslinked with a 15 components are mixed in the mixing system for at least variety of known covalent reacting crosslinking agents reac approximately 60 seconds. Once the mixing is complete, the tive with the hydroxyl functionality of large polysaccharide product is transferred to a packaging container where solidi molecules and can also be crosslinked using divalent, triva fication takes place. In an exemplary embodiment, the cast lent or polyvalent metal ions. Such crosslinked Xanthan gels composition begins to harden to a solid form in between are disclosed in U.S. Pat. No. 4,782,901, which is herein approximately 1 minute and approximately 3 hours. Particu incorporated by reference. Suitable crosslinking agents for larly, the cast composition begins to harden to a solid form Xanthan materials include, but are not limited to: metal in between approximately 1 minute and approximately 2 cations such as Al--3, Fe+3, Sb-i-3, Zr-4 and other transition hours. More particularly, the cast composition begins to metals. Examples of Suitable commercially available Xan harden to a solid form in between approximately 1 minute thans include, but are not limited to: KELTROL(R), KEL 25 and approximately 20 minutes. ZANOR AR, KELZANR D35, KELZANR, S, KELZANR) By the term "solid, it is meant that the hardened com XZ., available from Kelco Division of Merck, San Diego, position will not flow and will substantially retain its shape Calif. Known organic crosslinking agents can also be used. under moderate stress or pressure or mere gravity. The A preferred crosslinked Xanthan is KELZANR) AR, which degree of hardness of the solid cast composition may range provides a pseudoplastic use solution that can produce large 30 from that of a fused solid product which is relatively dense particle size mist or aerosol when sprayed. and hard, for example, like concrete, to a consistency Methods of Manufacture characterized as being a hardened paste. In addition, the In general, a Solid detergent composition of the present term “solid refers to the state of the detergent composition invention can be created by combining the alkali metal under the expected conditions of storage and use of the Solid silicate, polycarboxylate polymer, Saccharide or Sugar alco 35 detergent composition. In general, it is expected that the hol, water, and any additional functional components and detergent composition will remain in Solid form when allowing the components to interact and Solidify. exposed to temperatures of up to approximately 100°F. and The alkali metal silicate, and additional functional com particularly up to approximately 120° F. ponents harden into Solid form due to the chemical reaction The resulting solid detergent composition may take forms of the metal silicate with the water. The solidification 40 including, but not limited to: a cast solid product; an process may last from a few minutes to about six hours, extruded, molded or formed solid pellet, block, tablet, depending on factors including, but not limited to: the size powder, granule, flake; or the formed solid can thereafter be of the formed or cast composition, the ingredients of the ground or formed into a powder, granule, or flake. In an composition, and the temperature of the composition. exemplary embodiment, extruded pellet materials formed by The solid detergent compositions may be formed using a 45 the solidification matrix have a weight of between approxi batch or continuous mixing system. In an exemplary mately 50 grams and approximately 250 grams, extruded embodiment, a single- or twin-screw extruder is used to Solids formed by the composition have a weight of approxi combine and mix one or more cleaning agents at high shear mately 100 grams or greater, and solid block detergents to form a homogeneous mixture. In some embodiments, the formed by the composition have a mass of between approxi processing temperature is at or below the melting tempera 50 mately 1 and approximately 10 kilograms. The Solid com ture of the components. The processed mixture may be positions provide for a stabilized source of functional mate dispensed from the mixer by forming, casting or other rials. In some embodiments, the Solid composition may be Suitable means, whereupon the detergent composition hard dissolved, for example, in an aqueous or other medium, to ens to a solid form. The structure of the matrix may be create a concentrated and/or use solution. The Solution may characterized according to its hardness, melting point, mate 55 be directed to a storage reservoir for later use and/or rial distribution, crystal structure, and other like properties dilution, or may be applied directly to a point of use. according to known methods in the art. Generally, a solid In certain embodiments, the Solid detergent composition detergent composition processed according to the method of is provided in the form of a unit dose. A unit dose refers to the invention is substantially homogeneous with regard to a solid detergent composition unit sized so that the entire the distribution of ingredients throughout its mass and is 60 unit is used during a single washing cycle. When the Solid dimensionally stable. detergent composition is provided as a unit dose, it is In an extrusion process, the liquid and solid components typically provided as a cast Solid, an extruded pellet, or a are introduced into final mixing system and are continuously tablet having a size of between approximately 1 gram and mixed until the components form a substantially homoge approximately 50 grams. neous semi-solid mixture in which the components are 65 In other embodiments, the Solid detergent composition is distributed throughout its mass. The mixture is then dis provided in the form of a multiple-use solid, such as a block charged from the mixing system into, or through, a die or or a plurality of pellets, and can be repeatedly used to US 9,598,660 B2 19 20 generate aqueous detergent compositions for multiple wash ppm of at least one saccharide or Sugar alcohol, and between ing cycles. In certain embodiments, the Solid detergent about 10% and about 70% by weight water. When a poly composition is provided as a cast Solid, an extruded block, saccharide is present, a Suitable concentration range for at or a tablet having a mass of between approximately 5 grams least one polysaccharide is between about 10 ppm and about and approximately 10 kilograms. In certain embodiments, a 200 ppm. When sodium carbonate is present, a suitable concentration range for sodium carbonate is between about multiple-use form of the Solid detergent composition has a 1 ppm and about 1000 ppm. mass between approximately 1 kilogram and approximately The Solid detergent concentrate can contain an effective 10 kilograms. In further embodiments, a multiple-use form concentration of the at least one alkali metal silicate and of the Solid detergent composition has a mass of between optionally sodium carbonate so that use composition has a approximately 5 kilograms and about approximately 8 kilo 10 pH of at least about 9. grams. In other embodiments, a multiple-use form of the Solid detergent composition has a mass of between about EXAMPLES approximately 5 grams and approximately 1 kilogram, or between approximately 5 grams and approximately 500 The present invention is more particularly described in the grams. 15 following examples that are intended as illustrations only, Although the detergent composition is discussed as being since numerous modifications and variations within the formed into a solid product, the detergent composition may Scope of the present invention will be apparent to those also be provided in the form of a paste. When the concen skilled in the art. Unless otherwise noted, all parts, percent trate is provided in the form of a paste, enough water is ages, and ratios reported in the following examples are on a added to the detergent composition Such that complete weight basis, and all reagents used in the examples were Solidification of the detergent composition is precluded. In obtained, or are available, from the chemical suppliers addition, dispersants and other components may be incor described below, or may be synthesized by conventional porated into the detergent composition in order to maintain techniques. a desired distribution of components. Materials Used Method of Using 25 Acusol 445ND: a polyacrylic acid, 97% active, available The detergent composition is a concentrate Solid which from Dow can be diluted with water, known as dilution water, to form Belclene 200: a 400-800 MW polymaleic acid, 50% a concentrate solution or a use Solution. In general, a active, available from Houghton Chemical Corporation concentrate refers to a composition that is intended to be Sucrose: C-D-glucopyranosyl (1->2) B-D-fructofurano diluted with water to provide a use solution; a use solution 30 side (chemical name) is dispersed or used without further dilution. The use solu Fructose: levulose, CHO tion can be used to clean Substrates Such as during ware Inulin: CoHo,2Os Washing. Maltose: Isomaltase, 4-O-O-D-Glucopyranosyl-D-glu In one example, the Solid detergent composition is diluted COS such that the use solution has sufficient detersivity. The 35 Lactulose: 4-O-B-D-Galactopyranosyl-f-D-fructofura typical dilution factor is between approximately 1 and OS approximately 10,000 but will depend on factors including Pluronic N3: an ethylene oxide/propylene oxide block water hardness, the amount of soil to be removed and the copolymer available from BASF Corporation, Florham like. In one embodiment, the solid detergent composition is Park, N.J. diluted at a ratio of between about 1:10 and about 1:1000 40 Sorbitol: D-glucitol concentrate to water. Particularly, the solid detergent com position is diluted at a ratio of between about 1:100 and Examples 1-6 about 1:5000 concentrate to water. More particularly, the solid detergent composition is diluted at a ratio of between The raw materials identified for each of Examples 1-6 in about 1:250 and 1:2000 concentrate to water. 45 Table 5 below were combined and mixed. Example 1 was a Suitable concentration ranges for the use solution include control containing no saccharide. Each of the remaining between about 10 ppm and about 1000 ppm of at least one Examples 2-6 included equal weight percentages of the alkali metal silicate, between about 5 ppm and about 200 identified saccharide. TABLE 5

Description Control EX #2 EX #3 EX fia. EX is EX #6

Water 33 31.7 31.7 31.7 31.7 31.7 Sodium Metasilicate Anhydrous 49 47.5 47.5 47.5 47.5 47.5 Acusol 445ND (97% active) 7 6.9 6.9 6.9 6.9 6.9 Belclene 200 (50% active) 6 5.9 5.9 5.9 5.9 5.9 Sodium Metasilicate 4 4 4 4 4 4 Pentahydrate Pluronic N3 1 1 1 1 1 1 Fructose () O 3 O O O O Sucrose () O O 3 O O O Inulin (polysaccharide) O O O 3 O O maltose O O O O 3 O Lactulose O O O O O 3

Total Wt 90 1OO 100 1OO 100 1OO 100 US 9,598,660 B2 21 Once thoroughly mixed, each example was then poured TABLE 7 into a 16 oz cylindrical high density polyethylene container with a line drawn around the circumference of the container Description EX#11 EX #12 EX #13 about 1.75 inches from the container bottom. The mixtures Water 29.9 29.9 29.9 were allowed to harden into capsules in the container. Once Sodium Metasilicate Anhydrous 36 36 36 Ash monohydrate 24.6 24.6 24.6 hardened, three diameter measurements were taken via Acusol 445ND (97% active) 4.5 4.5 4.5 caliper for each of the six containers corresponding to Belclene 200 (50% active) 3.5 3.5 3.5 Experiments 1-6 and then separately averaged to determine Sodium Metasilicate 4 4 4 an initial capsule diameter. Pentahydrate 10 Pluronic N3 1 1 1 The containers were then placed in an oven at 122°F. for Sucrose (disaccharide) O 2 O 5 weeks with additional diameter measurements taken once Sorbitol (Sugar alcohol) O O 2 a week to determine the average increase in Swelling capsule Total Wt 90 103.5 105.5 105.5 growth of each Example. FIGS. 1 and 2 are line graphs showing the results, which indicate that Examples 2-6 15 The containers containing the capsules were then heated containing equal weight percentages of various saccharides and measured as described with respect to Examples 1-6. exhibited reduced Swelling and diameter increase compared FIGS. 5 and 6 are line graphs showing the results, which to the control, which included no saccharide. In particular, indicate that Examples 12 and 13, which contained a sac Examples 2-6 experienced less than two percent Swelling charide, exhibited reduced diameter increase and Swelling over the five week test period. compared to control Example 11. In particular, Examples 12 and 13 experienced about 0.5% or less swelling over the five Examples 7-10 week storage period. Although the present invention has been described with Examples 7-10 set forth in Table 6 below were prepared 25 reference to preferred embodiments, workers skilled in the in the same manner as Examples 1-6 except that equal mole art will recognize that changes may be made in form and amounts of the saccharides were used. detail without departing from the spirit and scope of the invention. TABLE 6 The invention claimed is: 30 1. A solid detergent composition comprising: Description EX #7 EX #8 EX #9 EX #10 from about 25 wt % to about 70 wt % of at least one alkali Water 32.4 32.1 32.1 32.1 metal silicate; Sodium Metasilicate 48.4 48 48 48 from about 0.5 wt % to about 10 wt % of at least one Anhydrous Acusol 445ND 7.1 7 7 7 Saccharide or Sugar alcohol; (97% active) 35 from about 1 % to about 15 wt % of at least one Belcene 200 6.1 6 6 6 polycarboxylic acid polymer, and (50% active) from about 10 wt % to about 70 wt % water; Sodium Metasilicate 4 4 4 4 Pentahydrate wherein said Solid detergent composition is free of phos Pluronic N3 1 1 1 1 phorus; wherein the at least one saccharide comprises Fructose 1 O O O 40 a monosaccharide or disaccharide; and wherein if the (monosaccharide) composition is heated at a temperature of 122°F. for 5 Sucrose (disaccharide) O 1.9 O O maltose O O 1.9 O weeks, the Solid detergent composition is dimension Lactulose O O O 1.9 ally stable and has a growth exponent of less than 2%. 2. The composition of claim 1, wherein the at least one Total Mole % 100 1OO 100 1OO 45 saccharide comprises Sucrose, fructose or combinations MOLES OF S.6 S.6 S.6 S.6 thereof. SACCHARIDE ADDED milimoles millimoles millimoles millimoles 3. The composition of claim 1, wherein the at least one saccharide comprises sucrose. The containers containing the capsules were then heated 4. The composition of claim 1 wherein the at least Sugar and measured as described with respect to Example 1-6. 50 alcohol comprises Sorbitol. FIGS. 3 and 4 are line graphs showing the results, which 5. The composition of claim 1, wherein the polycarbox indicate that Examples 7-10 containing equal mole amounts ylic acid polymer comprises at least one maleic acid poly of various saccharides exhibited reduced diameter increase mer, at least one acrylic acid polymer or combinations and Swelling compared to control Example 1, which thereof. included no saccharide. In particular, Examples 7-10 expe 55 6. The composition of claim 1 consisting essentially of the rienced less than two percent swelling over the five week test at least one alkali metal silicate, the at least one saccharide period. or Sugar alcohol, water and the at least one polycarboxylic acid polymer. 7. The composition of claim 1, wherein the at least one Examples 11-13 60 alkali metal silicate is present in an amount between about 25% and about 60% by weight. Examples 11-13 set forth in Table 7 below were prepared 8. The composition of claim 1, further comprising sodium in the same manner as Examples 1-6 except Examples 11-13 carbonate, wherein the alkali metal silicate is present in a also included sodium carbonate. Example 11 was a control greater amount than the Sodium carbonate. which did not contain a saccharide, and Example 12 65 9. The composition of claim 8 consisting essentially of the included a saccharide, and Example 13 contained a Sugar at least one alkali metal silicate, the at least one saccharide alcohol. or Sugar alcohol, water, Sodium carbonate, and the at least US 9,598,660 B2 23 24 one polycarboxylic acid polymer, wherein if the composi 17. The method of claim 15, wherein the at least one tion is heated at a temperature of 122°F. for 5 weeks, the saccharide comprises sucrose. Solid detergent composition is dimensionally stable and has 18. The method of claim 15, wherein the at least one sugar a growth exponent of about 0.5% or less. alcohol comprises Sorbitol. 10. The composition of claim 1, further comprising from 5 about 15 wt % to about 40 wt % of sodium carbonate. 19. A Solid detergent composition comprising: 11. A method of forming a solid detergent composition from about 25 wt % to about 70 wt % of at least one alkali according to claim 1, the method comprising: metal silicate; combining the at least one alkali metal silicate, the at least from about 0.5 wt % to about 10 wt % of at least one one saccharide or Sugar alcohol, the at least one poly 10 Saccharide or Sugar alcohol; carboxylic acid polymer, and from about 15 wt % to about 40 wt % sodium carbonate; water to form a mixture; and forming a solid detergent composition from the mixture. from about 1 wt % to about 15 wt % of at least one 12. The method of claim 11, further comprising the step polycarboxylic acid polymer, and of forming the Solid detergent composition into a block, from about 10 wt % to about 70 wt % water; capsule, pellet or tablet. 15 wherein said Solid detergent comnosition is free of phos 13. The method of claim 11, wherein the at least one alkali phorus; wherein the at least one saccharide comprises metal silicate is present in an amount between about 25% a disaccharide; and wherein if the composition is and about 50% by weight. heated at a temperature of 122°F. for 5 weeks, the solid 14. The method of claim 11, wherein the at least one detergent composition is dimensionally stable and has saccharide or Sugar alcohol is present in an amount between a growth exponent of less than 0.9%. about 0.5% and about 7% by weight. 15. A method of cleaning a substrate, the method com 20. The composition of claim 19, wherein the at least one prising: saccharide comprises sucrose. mixing water with a solid detergent composition accord 21. The composition of claim 19, wherein the at least one ing to claim 1 to form a use Solution, wherein the use Sugar alcohol comprises Sorbitol. Solution comprises: 25 22. The composition of claim 19, wherein the polycar from about 10 ppm to about 1000 ppm of the at least one boxylic acid the comprises at least one maleic acid polymer, alkali metal silicate; at least one acrylic acid polymer or combinations thereof. from about 5 ppm to about 200 ppm of the at least one 23. The composition of claim 19 consisting essentially of Saccharide or Sugar alcohol; from about 10 ppm to about 200 ppm of the at least one polyacrylic acid 30 the at least one alkali metal silicate, the at least one saccha polymer; and ride or Sugar alcohol, Sodium carbonate, water and the at contacting the Substrate with the use solution. least one polycarboxylic acid polymer, wherein if the com 16. The method of claim 15, wherein the use solution position is heated at a temperature of 122°F. for 5 weeks, the further comprises sodium carbonate and the Sodium carbon Solid detergent composition is dimensionally stable and has ate is present in a lesser amount than the at least one alkali 35 a growth exponent of about 0.5% or less. metal silicate. k k k k k