CA1251710A - Particulate built nonionic synthetic organic detergent composition - Google Patents
Particulate built nonionic synthetic organic detergent compositionInfo
- Publication number
- CA1251710A CA1251710A CA000482675A CA482675A CA1251710A CA 1251710 A CA1251710 A CA 1251710A CA 000482675 A CA000482675 A CA 000482675A CA 482675 A CA482675 A CA 482675A CA 1251710 A CA1251710 A CA 1251710A
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- detergent
- nonionic
- bicarbonate
- builder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3711—Polyacetal carboxylates
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure A particulate built nonionic synthetic organic detergent composition includes a detersive proportion of a nonionic synthetic organic detergent and a building proportion, in combination, of a polyacetal carboxylate builder for the nonionic detergent, and carbonate, bicarbonate and zeolite builders for such nonionic detergent. Such compositions may readily be made by adding polyacetal carboxylate builder to the formula of a control detergent composition, with corresponding diminutions in proportions of other component(s), and have detersive powers superior to such control despite the decrease in proportions present of detergent and other builders. Preferably, certain nonionic detergents, polyacetal carboxylate builders, carbonate, bicarbonate and zeolite, in certain proportions, are employed to make a product of better detergency and physical characteristics, e.g., flowability. Also disclosed are processes for manufacturing the described detergent compositions, in which processes spray dried builder base beads, containing carbonate, bicarbonate and zeolite builder salts, have nonionic detergent and polyacetal carboxylate builder (sometimes with additional zeolite) mixed with or applied to them. Additionally described are pump able and sprayable compositions of poly-acetal carboxylate builder in normally solid, liquid nonionic detergent at elevated temperature, which compositions are suitable for applying the nonionic detergent and polyacetal carboxylate builder (sometimes with additional zeolite being present) to the spray dried carbonate-bicarbonate-zeolite base beads, preferably as a spray impinging on moving surfaces of such beads.
Description
~25~q~
This invention relates to a particulate built nonionic synthetic organic detergent composition. More particularly, it relates to such a composition con~aining a building proportion, in combination, ~f polyacetal carboxylate and carbonate, bicarbonate and zeolite builders for the nonionic detergent. The invention also includes processes for manufacturing such products.
Particulate nonionic detergent products are known wherein base beads, comprised mostly of inorganic builder salt(s), e.g., carbonates, bicarbonate and zeolites, obtain-ed by spray drying an aqueous crutcher mix or slurry, have normally solid nonionic detergent in liquid state ab~orbed by them, to produc~ free flowing particulate compositions.
Polyacetal carboxylate builder sal~s suitable for use as builders with various organic detergents, primarily anionic organic detergents, have been described in the literature and in various U.S. and foreign patents. However, before the present invention, particulate built nonionic synthe ic organic detergent compositions containing carbonate, bi carbonate and zeolite builder salts and polyacetal carboxylate -- 3 ~
9~25~L7~0 in a total building proportion had not been disclosed and the advantages of such compositions and of processes for their manufacture,wherein the polyacetal carboxylate and nonionic detergent were applied to base beads of carbonate, bi-carbonate and zeolite builder salts,were not known.
Particulate nonionic detergent compositions in which the nonionic detergent is applied in liquid state to porous base beads containing carbonate, bicarbonate and zeolite builder salts are referred to generally in U.S. patent 4,269,722, and such compositions have been marketed under the trademark FRESH STAR ~. They are especially useful as non-phosphate or limited phosphate content detergents in those geographical or political areas where high phosphate content detergent compositions are prohibited. Polyacetal carboxylates are described in U.S. patents 4,144,226 and 4,315,092. U.S.
patents 4,146,495 and 4,219,437 claim detergent compositions containing the polyacetal carboxylate builder (4,146,495) and similar compositions con~aining keto dicarboxylates (4,219,437), which can often be employed in replacement of the polyacetal carboxylates. Various other patents on similar builders include 4,141l676; 4,169,934; 4,201,858;
4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,~22;
4,233,423; 4,302,564; and 4,303,777. Also relevant are European patent applications Nols. 0 015 024; 0 421 491; and 0 063 399. Although in some such patents and/or applications ~25~7~
there are included broad teachings that polyacetal carboxylates may be included in various types of detergent compositions, and although some such polyacetal carboxylates are described as components of compositions containing nonionic detergents and cationic softening agents, none of the references or combinations thereof describes or suggests such polyacetal carboxylates as components of the nonionic detergents of the present invention and none teaches the obtaining of the described improved detergency of the invented compositions and the free flowing nature of the products made. Also, the present manufacturing processes are not described or fairly suggested in any such reference or in any combination of the references.
In accordance with the present invention a p~rticulate built nonionic synthetic organic detergent composition comprises a detersive proportion of a nonionic synthetic organic detergent, and a building proportion, in combination, of a polyacetal carboxylate builder for the nonionic detergent and carbonate, bicarbonate an~ zeolite builders for tne nonionic detergent, wherein the nonionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 3,50~ to 10,000, the alkali metal carbonate is sodium carbonate, the alkali metal bicarbonate is sodium bicarbonate and the zeolite lS Zeolite A, X or Y, and the proportions of components are $rom 5 to 35% of nonionic detergent and from 30 to ~5% of a combination of polyacetal carboxylate, alkali l ~
~25~7~ 62301-1316 metal carbonate preferably sodium carbonate, alkali metal bicarbonate preferably, sodium bicarbonate, and zeolite builders, with the ratio of polyacetal carboxylate to the combination of alkali metal carbonate, alkali metal bicarbonate and zeolite builders being within the range of 1:5 to 2:1 the ratio of alkali metal carbonate to alkali metal bicarbonate being within the range of 1:2 to 4:1 and the ratio of zeolite to the combination of sodium carbonate and sodium bicarbonate being within the range of 3:1 to 1:3, and with the balance of the composition, if any, a substance selected from the group consisting of a filler, other builder, adjuvant and moisture. Also within the invention are processes for making such particulate detergents.
- 5a -~L25~7~
The polyacetal carboxylate may be considered to be that described in U.S. patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula Rl (CHO)n - R2 COOM
wherein M is ~cl~ct~d fronl the cJrou~ consisting of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetra-alkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and Rl and R2 are any chemically stable groups which ~tabilize the polymer against rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, n i.s from 50 to 15 200, Rl is HCO- or H3C-CO-or a mixture thereof, R2 is CH2c~3 -CH
a~d n averages from 20 to 100, more preferably 30 o 80.
The calculated weight average molecular weights of the polymers will normally be within the range of 2,~00 to ~ 25~7~(3 20,000, preferably 3,500 to 10,000 and more prefer~bly 5,000 to 9,000, e.g., about 8,000.
Although the preferred polyacetal carboxylate~
have been described above, it is to be understood that they may be wholly or ~arti~lly replaced by other such polyacetal carboxylate or r~ organic builder s~lts descrihed in the pr~viou~ly ~it~ rlt~ on ~uch compounds, processes for the m~nuf~cture th~r~of ~n~ cvmL~o~itions in which they are employed. Also, the chain terJninatin~ groups described in the Yarious patents, especially U.S. 4,144,226, may be utilized, providin~ that they have the desired stabilizing properties, which allow the mentioned builders to be depoly-merized in acid media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, ~uch as wa~hin~ ~olutions.
The carbonate and bicarbonate builders are highly preferably sodium salt~ but other water soluble alkali metal carbonatesand bicarbon~tesmay also be employed, at least in part, ~uch as ~hose of potassium. Such may be in anhydrou~, hyd~ated or partially hydrated state. Sodium sesquicarbonat~
may be used in partial or complete replacements of the carbonate and bicarbonate. One of the advantages of the pre~ent invention is tha~ the sodium carbona~e found in ~uilde~ ua~ the available polyacetal carboxyla~e, is useful as a builder in the detergent compositions made.
The zeoli~e component will usually be of the formula (Na2O)x-(Al2O3)y-(SiO2)-~ H2O,wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to ~25~7~0 3 or about 2 and w is from 0 to 9, preferably 2.5 to 6. Such zeolites are cation exchanging and have an exchange capacity for calcium ion from about 200 to 400 or more milligram equi-valents of calcium carbonate hardness per gram. They will preferably be hydrated to the extent of 5 to 30%, preferably 10 to 25% moistur~, e.g., about 20~ thereof. Zeolite A is preferred (X and Y are also useful) and of such zeolite, 4A
is most preferred. Particle sizes of the zeolite(s) will usually be 100 to 400 mesh (or sieve number), preferably 140 or 200 to 325 mesh but their ultimate sizes will be submicron.
The fifth component of the present detergent compositions is a nonionic synthetic organic detergent or a mixture of such detergents. While various suitable nonionic detergents having the desired detersive properties and physical characteristics (normally solid, at room tempera-ture, but liquefiable so as to be capable of being applied to base beads in liquid form) may be employed, at least as a part of such detergent content of the invented compositions, very preferably the nonionic detergent will be a csndensation product of ethylene oxide and a higher fatty alcohol. The ethylene oxide content of such detergents will be within the range of 3 to 20 moles, preferably 3 to 12 moles and more preferably 6 ~o 8 moles, e.g., about 6.5 or 7 moles of ethylene oxide, per mole of fatty alcohol, and the fatty alcohol will usually be of 10 to 18 carbon atoms, preferably averaging 12 to 15 carbon atoms, e.g., about 13 or 14 carbon atoms. Among other nonionic detergents that are also useful are the ethylene oxide condensation products of alkylphenols ~25~7~0 of 5 to 12 carbon atoms in the alkyl group, such as nonyl-phenol, in which the ethylene oxide content is from 3 to 30 moles per mole, and condensation products of ethylene oxide and propylene oxide, sold under the trademark Pluronic~
Although essentially anhydrous products can be manufactured and are useful, usually moisture will be present in the deterg~nt composition, either in free form or as a hydrate, such as hydrated sodium carbonate and hydrated zeolite. The presence of such hydrates can strengthen the detergent c~mposition particles and sometimes they facilitate dissolving of such particles in the wash water. For such reasons, and to facilitate manufacturing, moisture is pr -ferably present in the product.
In addition to the mentioned components, other materials, such as a supplementing builder (sodium silicate) and adjuvants may be employed. Also, in some cases condensa-tion products of higher fatty alcohol and ethylene oxide of greater ethylene oxide contents than 20 moles per mole may be employed in substitution for some o the condensation products of lesser ethylene oxide con~ent. Thus, if it is desirable to further improve flowability of a preferred product a harder nonionic component, such as one of 21 to 50 ethylene oxide groups per mole, may be utiliz~d in part, in which case it will desirably be from 1 to 50%, usually more preferably from 5 to 25% of the total nonionic detergent content. Also, sodium silicate, which has a supplemPnting building action and aids in inhibiting corrosion of aluminum items in wash water containing the detergent composition, _ g _ ~.25~7~
will be of Na2O:SiO2 ratio in the range of about 1:1.6 to 1:3, preferably 1:2 to 1:2.6, e.g., 1:2.35 or 1:2.4.
Among the va~ious adjuvants that may be employed are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, antioxidants, fluorescent brighteners, buffers, fungicides, germicides, and flow promoting agents. If desired, fillers, such as sodium sulfate and/or sodium chloride, may also be present. Also among the "adjuvants"
are included various fillers and impurities in other components of the compositions, such as Na2CO3 in the polyacetal carboxylate (Builder U).
The proportions of the various components that will result in the desired improved detersi~e properties (previously mentioned) will normally be from 5 to 35~ of nonionic deter~ent, and from 30 to 95~ of a combination of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders. The ratio of the polyacetal carboxylate to combined carbonate, bicarbonate and zeolite will be in the range of 1:5 to 2:1, preferably 1:5 to 3:2, and more preferably 1:4 to 1:}, e.g., about 1:2.4. Any balances of such compositions will be filler(s), other builder(s), adjuvant(s) and moisture.
Usually the nonionic detergent content will be at least 5 of the product and the carbonate plus bicarbonate plus zeolite builders content will be at least 20%, preferably at least 35~ thereof. The nonionic detergent content will preferably be 10 to 30%, more preferably 10 to 20%, e.g., about 16%, the polyacetal carboxylate will preferably be 10 to 40%, more preferably 10 to 25%, e.g., about 18 or 22%, and the total of carbonate, bicarbonate and zeolite - -~ z5~
will preferably be from 35 to 80~, more preferably 50 to 70%, e.g., about 62~ of the detergent composition. The ratio of carbonate to bicarbonate will be within the range of 1:2 to 4:1, preferably 1:1 to 3:1 and more preferably 1:1 to 2:1, e.g., about 1:l.4. The ratio of zeolite to the combination of carbonate and bicarbon~te will normally be within the range of 3:1 to 1:3, preferably 1:2 to 2:1, e.g., about 0.9. Prefer-ably the percentages of carbonate, bicarbonate and zeolite will be within the ranges of 5 to 25%, 3 to 20~ and 8 to 35~, respectively, more preferably 10 to 20%, 5 to 15% and 10 to 25~, respectively, e.g., about 14~, about 10% and about 21~, respectively. The moisture content of the product will usual-ly be from 1 to 20~, preferably 2 to 15~ and more preferably from 3 to 8~, e.g., about 4 or 53. Such moisture content includes that which is removable from the product in standard oven drying (105C. for two hours). The sodium silicate content, when sodium silicate is present, will be from 1 to 8~, preferably 5 to 15~ and more preferably 5 to 10%, e.g., about 8~. The total percentage of adjuvants may range from 0 to 20% but normally will be at the lower end of such range, 1 to 10%, preferably 2 to 6~, e.g., about 4 or 5%, with individual adjuvant percentages usually being from 0.1 to 5~, preferably 0.2 to 3~. In the foregoing description and elsewhere in the specification the percentages of carbonate and bicarbonate given are on an "anhydrous" basis, and do not include any moisture that is removable by oven drying, as described above. However, the percen~ages of zeolite do include the water of hydration because at least some of it is not readily removable by heating. The content of filler(s) -- 11 ~
~5~7~() may be as high as 40% in some instances but usually, if filler is present, the proportion thereof will be in the range of 5 to 30%, often 10 to 25%.
The particulate detergent product of this invention may be made by the method described in U.S. patent 4,269,722 and U.S. patent 4,144,226. Following such method, an aqueous slurry is made which includes the particulate sodium carbonate, sodium carbonate and zeolite, sodium silicate, usually added as an aqueous solution, water, and any suitable fillers and adju-vants, such as fluorescen-t brightener and pigment, which are heat stable.Sodium sulfate has been found to adversely affect flowability of the detergent composition, when added to base beads with nonionic detergent, so its presence is sometimes avoided. In some instances the polyacetal carboxylate builder may be added in the crutcher but because it has sometimes been found to be of limited stability when processed at elevated temperature, such builder is often post-added. Generally the crutcher mix is at a solids conkent in the range of 40 to 70%
and is heated to a temperature in the range of 40 to 70C.
Anhydrous or hydrated bicarbonate and carbonate or other suit-able combined form thereof, such as sodium sesquicarbonate, may be employed. However, a major proportion of the nonionic deter-gent component wil~ not be present in the crutcher; instead, it will be post-added~ and preferably the proportion of nonionic detergent in the crutcher will be limited to about 4%, prefer-ably 2% or less~ (on a final product basis), and most preferably, none, so as to avoid loss of such detergent during the spray drying operation. If agitation to produce uniformity of the slurry is difficult, because of excessive gelation or thickening of the ~25~
mix, viscosity control agents, such as citric acid, magnesium sulate and/or magnesium citrate may be employed. Such thin-ning agents will be considered to be within the group designated "adjuvants". After thorough mixing in the crutcher which may take from 10 minutes to an hour, the crutcher slurry is pumped to a conventional spray drying tower, either con-current or countercurrent, in which it is dried by heated drying air at a temperature in the range of 200 to 500C.
preferably 200 to 350C. if the mix contains polyacetal carboxylate, to produce globular spray dried particles of ~ sizes in the range of No's. 8 to 100 sieves, U.S. Sieve ; SeriesO Such base beads are desirably porous, so as to be capable of absorbing nonionic detergent, and such porosity is due at least in part to the decomposition of bicarbonate to carbonate during spray drying, which produces "puffing" carbon dioxide. Normally, from 20 to 80% of the bicarbonate converts to carbonate, depending on spray tower conditions.
~ he porous base beads resulting are introduced into a suitable batch or continuous mixer or blender, such as an inclined rotary drum (batch), in which they are post sprayed at a suitable temperature at which the nonionic detergent is liquid, usually in the range of 45 to 60C., preferably 45 to 50C. In one embodiment of the invented process all the nonionic detergent, in liquid state and pre-ferably at elevated temperature in the described preferredrange, is sprayed onto the moving surfaces of th~ mass of base beads by means of an atomizing nozzle of conventional type, and during mixing it penetrates into the interiors of the beads, with some of nonionic detergent being near the ~Z5~1.7~(~
surface thereof. Then, without cooling to the solidification point of the detergent, the polyacetal carboxylate builder, in finely divided powdered form, as of particle sizes in the range of 200 to 400 mesh (although coarser particles as large as No. 100, U.S. Sieve Series, may also be used), is dusted onto the moving base beads, which now contain absorbed nonionic detergent. Some of the finely divided polyacetal carboxylate particles are drawn into the interstices and cavities of the beads by the still liquid nonionic detergent and others adhere to such detergent near the surfaces of the beads, and are held to the beads as the detergent is cooled to solidification. In such operation the polyacetal carboxylate which is held to the base beads inhibits the production of tacky product. At the same time, the holding of it to th~
beads prevents stratification of the product in its end use package during shipment and storage.
Various adjuvants of the types that would normally be post-added, such as enzyme powders and perfumes, may be added with the polyacetal carboxylate powder or before or 2Q after the powder addition. Usually, as with the nonionic detergent, it is preferred to spray liquid components onto the surfaces of the intermediate detergent composition particles but in some instances, as is also the case with application of the nonionic detergent in liquid state to the base beads, spraying is unnecessary and dripping of the liquid also serves to distribute it satisfactorily and to -- lq --~:25~7~C~
promote absorption of it into the porous particles. Powdered materials being added are preferably in finely divided powdered form, as described above for the polycarboxylate builder, but other particle size ranges may also be utilized (as they may be for the builder), although in such cases the results may not ~e as satisfactory. Also, instead of spraying the liquld material onto spray dried base beads for absorption, in some instances one may apply the liquid to granular (not spray dried) mixed carbonate, bicarbonate and zeolite particles, but such is not usually as satisfactory because such particles do no~ normally have the absorbing capacity of spray dried base beads and are less uniform.
Instead of having post-applied powdered polyacetal carboxylate particles adhered to liquid detergent that has been applied to base beads, in another and preferred process of this invention the builder is applied to the base beads as a dispersion of the polyacetal carboxylate in the normally solid nonionic detergent at elevated temperature and in liquid state. In such application, some of the polyacetal carboxylate builder may be dissolved in the liquid nonionic detergent but normally more of it is dispersed therein, preferably in finely divided particles, such as those small~r than 200 mesh, and preferably larger than 400 mesh. In such applications the base beads may be heated initially to a temperature like that of the liquid state detergent being applied but it has been found that although theoretically i25~7~0 such an operation would be thought to promote greater absorp-tion o~ the detergent and polyacetal carboxylate builder, in practice it is sufficient for the base beads to be at room temperature, at which satisfactory absorption and quick S cooling of the product result. The dispersion of polyacetal carboxylate builder particles in liquid state nonionic detergent is preferably ~prayed onto a moving bed of base beads but sometimes spraying is unnecessary, and mere dripping of the liquid medium onto the base beads is satis~actory, and in some instances it is enough merely to admix the base beads and the dispersion together without any concern fox the mode of application of the liquid dispersion to the base beads being required.
The temperature of the dispersion of polyacetal carboxylate particles in a nonionic detergent may be such as has been found to be suitable for use in the application process described. Normally such temperature will be in the range of 45 to 95C. but preferably, so as better to main-tain stability of the polyacetal carboxylate and to promote quicker cooling after application thereof to the base parti-cles, the temperature of application will be in the range of 45 to 60C., most preferably about 45 to 53 or 55C.
However, this depends on the solidification point of the no~ionic detergent, which will be the same as or low~r than the lowest temperature of such a range. Of cours~, with ~253L7~L0 higher melting nonionic detergents the lower limit of the range will be adjusted accordingly, usually being at least 2 and preferably at least 5 or 10 higher than the solidifica-tion point. The polyacetal car~oxylate will preferably be of particle sizes, substantially all (usually msre ~han 90~, preferably more than 95~ and more preferably more than 9~) of which are no larg~r than that which will pass through No. 200 sieve, U.S. Sieve Series (or a 200 mesh sieve).
~ow~ver, larger sized particles may be employed but generallysuch are not larger than 100 or 160 mesh. Preferably the particles will be in the 200 to 400 mesh range, e.g., 200 to 325 mesh, to promote penetrations into interstices of the base beads and to promote better holdings to the surfaces thereof.
In the dispersions mentioned, in which some of the polyacetal carboxylate may be in solution, the proportion of polyacetal carboxylate to nonionic detergent will normally be in the range of 1:20 to 3:2, preferably 1:10 to 1;1 and more preferably 1:2 to 1:1. However, such proportions may be adjusted, depending on the formula proportions of the polyacetal carboxylate and nonionic detergent desired to be in the end product. Still, normally no more than three parts of polyacetal carboxylate will be present with ~wo parts of nonio~ic detergent, and preferably such ~pper limit will be 1:1. If more polyacetal carboxylate is desired in the product formula it may be po5t-applied, as previously described, ~Z5~7~C~
after absorption of some of the polyacetal carboxylate and the liquid state nonionic detergent. While other materials, including particulate materials, such as enzymes, may be post-added, sometimes they may also be dissolved and/or dispersed in the nonionic detergent, with the polyacetal carboxylate and m~y be applied to the base beads together with such builder and detergent. Also, some or all of the zeolite, such as 2 to 20~ of the composition, may be dispersed in the nonionic detergent with the polyacetal carboxylate, and/or may be post-applied to improve flow properties of the product.
In some cases, some (sometimes all) of the poly-acetal carboxylate may be spray dried with the carbonate, bicarbonate and zeolite builders but in such instances the employment of mild conditions will be desired, with special care being taken not to allow buildup cf p~oduct on the spray tower interior walls, where the polyacetal carboxylate could be decomposed. So long as the spray tower conditions are such that the bead temperatures do not rise to a destabilizing temperature for the polyacetal carboxylate employed, spray drying is feasible but because this cannot always be assured in commercial spray drying processes, as a practical matter it is often preferable to post-apply the polyacetal carboxylate.
The product of the formulations given, produced by any of the methods described, is satisfactorily free flowing, ~2S~710 non-tacky and non-caking despite its contents of nonionic detergent and polyacetal carboxylate. The particles thereof are regular in shape, approximately the spherical, and the product is of desired bulk density (higher than the bulk density of usual spray dried products, which tends to be in the range of 0.25 to 0.4 g./ml.), normally being in the range of about 0.5 to 0.8 g./ml., such as 0.6 to 0.7 g./ml.
Thus, smaller packages may be employed, creating more avail-able supermarket shelf space and facilitating home laundry storage. The detergent compositions made are excellent de~ergents, with improved cleaning power against a variety of soils. Their detergencies are greater than that of a control detergent without the polyacetal carboxylate. Surprisingly, the detergency of the present compositions is better than that of a control, despite the fact that the proportion of nonionic detergent in the control is higher. It should be pointed out that the total proportion of builder is great~r in the "experimental" product, but ~hen too, the proportions of carbonate, bicarbonate, zeolite and silicate builders are lower.
The following ~xamples illustrate but do not limit the invention. Unless otherwise indicated all temperatures are in C. and all parts are by weight in the examples, elsewhere in the specification, and in the claims.
3L~5~L710 Component Parts Sodium carbonate (anhydrous) 13.6 Sodium bicarbonate 9.7 Sodium zeolite (Zeolite 4A, 20~ hydrate) 20.7 ~igher fatty alcohol polyethoxylate nonionic 15.9 detergent(l) Sodium polyacetal carboxylate [Builder ~] 23.1 Sodium silicate solids (Na2O:SiO2 = 1:2.4) 8.2 10 Magnesium sulfate (anhydrous) 1.17 Sodium citrate (viscosity regulating agent) 0.45 Moisture 4.0 Enzyme powder (proteolytic enzyme, 200 mesh) 1.52 Fluorescent brightener (Tinopal 5B~ Conc.) 1.32 15 Blue pigment (~ltramarine blue) 0.15 Perfume 9.19 100.O
(1) Condensation product of 6.5 moles of ethylene oxide and one mole of higher fatty alcohol of 12 - 13 carbon atoms sold as Neodol 23-6.5 by Shell Chemical Company
This invention relates to a particulate built nonionic synthetic organic detergent composition. More particularly, it relates to such a composition con~aining a building proportion, in combination, ~f polyacetal carboxylate and carbonate, bicarbonate and zeolite builders for the nonionic detergent. The invention also includes processes for manufacturing such products.
Particulate nonionic detergent products are known wherein base beads, comprised mostly of inorganic builder salt(s), e.g., carbonates, bicarbonate and zeolites, obtain-ed by spray drying an aqueous crutcher mix or slurry, have normally solid nonionic detergent in liquid state ab~orbed by them, to produc~ free flowing particulate compositions.
Polyacetal carboxylate builder sal~s suitable for use as builders with various organic detergents, primarily anionic organic detergents, have been described in the literature and in various U.S. and foreign patents. However, before the present invention, particulate built nonionic synthe ic organic detergent compositions containing carbonate, bi carbonate and zeolite builder salts and polyacetal carboxylate -- 3 ~
9~25~L7~0 in a total building proportion had not been disclosed and the advantages of such compositions and of processes for their manufacture,wherein the polyacetal carboxylate and nonionic detergent were applied to base beads of carbonate, bi-carbonate and zeolite builder salts,were not known.
Particulate nonionic detergent compositions in which the nonionic detergent is applied in liquid state to porous base beads containing carbonate, bicarbonate and zeolite builder salts are referred to generally in U.S. patent 4,269,722, and such compositions have been marketed under the trademark FRESH STAR ~. They are especially useful as non-phosphate or limited phosphate content detergents in those geographical or political areas where high phosphate content detergent compositions are prohibited. Polyacetal carboxylates are described in U.S. patents 4,144,226 and 4,315,092. U.S.
patents 4,146,495 and 4,219,437 claim detergent compositions containing the polyacetal carboxylate builder (4,146,495) and similar compositions con~aining keto dicarboxylates (4,219,437), which can often be employed in replacement of the polyacetal carboxylates. Various other patents on similar builders include 4,141l676; 4,169,934; 4,201,858;
4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,~22;
4,233,423; 4,302,564; and 4,303,777. Also relevant are European patent applications Nols. 0 015 024; 0 421 491; and 0 063 399. Although in some such patents and/or applications ~25~7~
there are included broad teachings that polyacetal carboxylates may be included in various types of detergent compositions, and although some such polyacetal carboxylates are described as components of compositions containing nonionic detergents and cationic softening agents, none of the references or combinations thereof describes or suggests such polyacetal carboxylates as components of the nonionic detergents of the present invention and none teaches the obtaining of the described improved detergency of the invented compositions and the free flowing nature of the products made. Also, the present manufacturing processes are not described or fairly suggested in any such reference or in any combination of the references.
In accordance with the present invention a p~rticulate built nonionic synthetic organic detergent composition comprises a detersive proportion of a nonionic synthetic organic detergent, and a building proportion, in combination, of a polyacetal carboxylate builder for the nonionic detergent and carbonate, bicarbonate an~ zeolite builders for tne nonionic detergent, wherein the nonionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 3,50~ to 10,000, the alkali metal carbonate is sodium carbonate, the alkali metal bicarbonate is sodium bicarbonate and the zeolite lS Zeolite A, X or Y, and the proportions of components are $rom 5 to 35% of nonionic detergent and from 30 to ~5% of a combination of polyacetal carboxylate, alkali l ~
~25~7~ 62301-1316 metal carbonate preferably sodium carbonate, alkali metal bicarbonate preferably, sodium bicarbonate, and zeolite builders, with the ratio of polyacetal carboxylate to the combination of alkali metal carbonate, alkali metal bicarbonate and zeolite builders being within the range of 1:5 to 2:1 the ratio of alkali metal carbonate to alkali metal bicarbonate being within the range of 1:2 to 4:1 and the ratio of zeolite to the combination of sodium carbonate and sodium bicarbonate being within the range of 3:1 to 1:3, and with the balance of the composition, if any, a substance selected from the group consisting of a filler, other builder, adjuvant and moisture. Also within the invention are processes for making such particulate detergents.
- 5a -~L25~7~
The polyacetal carboxylate may be considered to be that described in U.S. patent 4,144,226 and may be made by the method mentioned therein. A typical such product will be of the formula Rl (CHO)n - R2 COOM
wherein M is ~cl~ct~d fronl the cJrou~ consisting of alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetra-alkylammonium groups and alkanolamine groups, both of 1 to 4 carbon atoms in the alkyls thereof, n averages at least 4, and Rl and R2 are any chemically stable groups which ~tabilize the polymer against rapid depolymerization in alkaline solution. Preferably the polyacetal carboxylate will be one wherein M is alkali metal, e.g., sodium, n i.s from 50 to 15 200, Rl is HCO- or H3C-CO-or a mixture thereof, R2 is CH2c~3 -CH
a~d n averages from 20 to 100, more preferably 30 o 80.
The calculated weight average molecular weights of the polymers will normally be within the range of 2,~00 to ~ 25~7~(3 20,000, preferably 3,500 to 10,000 and more prefer~bly 5,000 to 9,000, e.g., about 8,000.
Although the preferred polyacetal carboxylate~
have been described above, it is to be understood that they may be wholly or ~arti~lly replaced by other such polyacetal carboxylate or r~ organic builder s~lts descrihed in the pr~viou~ly ~it~ rlt~ on ~uch compounds, processes for the m~nuf~cture th~r~of ~n~ cvmL~o~itions in which they are employed. Also, the chain terJninatin~ groups described in the Yarious patents, especially U.S. 4,144,226, may be utilized, providin~ that they have the desired stabilizing properties, which allow the mentioned builders to be depoly-merized in acid media, facilitating biodegradation thereof in waste streams, but maintain their stability in alkaline media, ~uch as wa~hin~ ~olutions.
The carbonate and bicarbonate builders are highly preferably sodium salt~ but other water soluble alkali metal carbonatesand bicarbon~tesmay also be employed, at least in part, ~uch as ~hose of potassium. Such may be in anhydrou~, hyd~ated or partially hydrated state. Sodium sesquicarbonat~
may be used in partial or complete replacements of the carbonate and bicarbonate. One of the advantages of the pre~ent invention is tha~ the sodium carbona~e found in ~uilde~ ua~ the available polyacetal carboxyla~e, is useful as a builder in the detergent compositions made.
The zeoli~e component will usually be of the formula (Na2O)x-(Al2O3)y-(SiO2)-~ H2O,wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to ~25~7~0 3 or about 2 and w is from 0 to 9, preferably 2.5 to 6. Such zeolites are cation exchanging and have an exchange capacity for calcium ion from about 200 to 400 or more milligram equi-valents of calcium carbonate hardness per gram. They will preferably be hydrated to the extent of 5 to 30%, preferably 10 to 25% moistur~, e.g., about 20~ thereof. Zeolite A is preferred (X and Y are also useful) and of such zeolite, 4A
is most preferred. Particle sizes of the zeolite(s) will usually be 100 to 400 mesh (or sieve number), preferably 140 or 200 to 325 mesh but their ultimate sizes will be submicron.
The fifth component of the present detergent compositions is a nonionic synthetic organic detergent or a mixture of such detergents. While various suitable nonionic detergents having the desired detersive properties and physical characteristics (normally solid, at room tempera-ture, but liquefiable so as to be capable of being applied to base beads in liquid form) may be employed, at least as a part of such detergent content of the invented compositions, very preferably the nonionic detergent will be a csndensation product of ethylene oxide and a higher fatty alcohol. The ethylene oxide content of such detergents will be within the range of 3 to 20 moles, preferably 3 to 12 moles and more preferably 6 ~o 8 moles, e.g., about 6.5 or 7 moles of ethylene oxide, per mole of fatty alcohol, and the fatty alcohol will usually be of 10 to 18 carbon atoms, preferably averaging 12 to 15 carbon atoms, e.g., about 13 or 14 carbon atoms. Among other nonionic detergents that are also useful are the ethylene oxide condensation products of alkylphenols ~25~7~0 of 5 to 12 carbon atoms in the alkyl group, such as nonyl-phenol, in which the ethylene oxide content is from 3 to 30 moles per mole, and condensation products of ethylene oxide and propylene oxide, sold under the trademark Pluronic~
Although essentially anhydrous products can be manufactured and are useful, usually moisture will be present in the deterg~nt composition, either in free form or as a hydrate, such as hydrated sodium carbonate and hydrated zeolite. The presence of such hydrates can strengthen the detergent c~mposition particles and sometimes they facilitate dissolving of such particles in the wash water. For such reasons, and to facilitate manufacturing, moisture is pr -ferably present in the product.
In addition to the mentioned components, other materials, such as a supplementing builder (sodium silicate) and adjuvants may be employed. Also, in some cases condensa-tion products of higher fatty alcohol and ethylene oxide of greater ethylene oxide contents than 20 moles per mole may be employed in substitution for some o the condensation products of lesser ethylene oxide con~ent. Thus, if it is desirable to further improve flowability of a preferred product a harder nonionic component, such as one of 21 to 50 ethylene oxide groups per mole, may be utiliz~d in part, in which case it will desirably be from 1 to 50%, usually more preferably from 5 to 25% of the total nonionic detergent content. Also, sodium silicate, which has a supplemPnting building action and aids in inhibiting corrosion of aluminum items in wash water containing the detergent composition, _ g _ ~.25~7~
will be of Na2O:SiO2 ratio in the range of about 1:1.6 to 1:3, preferably 1:2 to 1:2.6, e.g., 1:2.35 or 1:2.4.
Among the va~ious adjuvants that may be employed are colorants, such as dyes and pigments, perfumes, enzymes, stabilizers, antioxidants, fluorescent brighteners, buffers, fungicides, germicides, and flow promoting agents. If desired, fillers, such as sodium sulfate and/or sodium chloride, may also be present. Also among the "adjuvants"
are included various fillers and impurities in other components of the compositions, such as Na2CO3 in the polyacetal carboxylate (Builder U).
The proportions of the various components that will result in the desired improved detersi~e properties (previously mentioned) will normally be from 5 to 35~ of nonionic deter~ent, and from 30 to 95~ of a combination of polyacetal carboxylate and carbonate, bicarbonate and zeolite builders. The ratio of the polyacetal carboxylate to combined carbonate, bicarbonate and zeolite will be in the range of 1:5 to 2:1, preferably 1:5 to 3:2, and more preferably 1:4 to 1:}, e.g., about 1:2.4. Any balances of such compositions will be filler(s), other builder(s), adjuvant(s) and moisture.
Usually the nonionic detergent content will be at least 5 of the product and the carbonate plus bicarbonate plus zeolite builders content will be at least 20%, preferably at least 35~ thereof. The nonionic detergent content will preferably be 10 to 30%, more preferably 10 to 20%, e.g., about 16%, the polyacetal carboxylate will preferably be 10 to 40%, more preferably 10 to 25%, e.g., about 18 or 22%, and the total of carbonate, bicarbonate and zeolite - -~ z5~
will preferably be from 35 to 80~, more preferably 50 to 70%, e.g., about 62~ of the detergent composition. The ratio of carbonate to bicarbonate will be within the range of 1:2 to 4:1, preferably 1:1 to 3:1 and more preferably 1:1 to 2:1, e.g., about 1:l.4. The ratio of zeolite to the combination of carbonate and bicarbon~te will normally be within the range of 3:1 to 1:3, preferably 1:2 to 2:1, e.g., about 0.9. Prefer-ably the percentages of carbonate, bicarbonate and zeolite will be within the ranges of 5 to 25%, 3 to 20~ and 8 to 35~, respectively, more preferably 10 to 20%, 5 to 15% and 10 to 25~, respectively, e.g., about 14~, about 10% and about 21~, respectively. The moisture content of the product will usual-ly be from 1 to 20~, preferably 2 to 15~ and more preferably from 3 to 8~, e.g., about 4 or 53. Such moisture content includes that which is removable from the product in standard oven drying (105C. for two hours). The sodium silicate content, when sodium silicate is present, will be from 1 to 8~, preferably 5 to 15~ and more preferably 5 to 10%, e.g., about 8~. The total percentage of adjuvants may range from 0 to 20% but normally will be at the lower end of such range, 1 to 10%, preferably 2 to 6~, e.g., about 4 or 5%, with individual adjuvant percentages usually being from 0.1 to 5~, preferably 0.2 to 3~. In the foregoing description and elsewhere in the specification the percentages of carbonate and bicarbonate given are on an "anhydrous" basis, and do not include any moisture that is removable by oven drying, as described above. However, the percen~ages of zeolite do include the water of hydration because at least some of it is not readily removable by heating. The content of filler(s) -- 11 ~
~5~7~() may be as high as 40% in some instances but usually, if filler is present, the proportion thereof will be in the range of 5 to 30%, often 10 to 25%.
The particulate detergent product of this invention may be made by the method described in U.S. patent 4,269,722 and U.S. patent 4,144,226. Following such method, an aqueous slurry is made which includes the particulate sodium carbonate, sodium carbonate and zeolite, sodium silicate, usually added as an aqueous solution, water, and any suitable fillers and adju-vants, such as fluorescen-t brightener and pigment, which are heat stable.Sodium sulfate has been found to adversely affect flowability of the detergent composition, when added to base beads with nonionic detergent, so its presence is sometimes avoided. In some instances the polyacetal carboxylate builder may be added in the crutcher but because it has sometimes been found to be of limited stability when processed at elevated temperature, such builder is often post-added. Generally the crutcher mix is at a solids conkent in the range of 40 to 70%
and is heated to a temperature in the range of 40 to 70C.
Anhydrous or hydrated bicarbonate and carbonate or other suit-able combined form thereof, such as sodium sesquicarbonate, may be employed. However, a major proportion of the nonionic deter-gent component wil~ not be present in the crutcher; instead, it will be post-added~ and preferably the proportion of nonionic detergent in the crutcher will be limited to about 4%, prefer-ably 2% or less~ (on a final product basis), and most preferably, none, so as to avoid loss of such detergent during the spray drying operation. If agitation to produce uniformity of the slurry is difficult, because of excessive gelation or thickening of the ~25~
mix, viscosity control agents, such as citric acid, magnesium sulate and/or magnesium citrate may be employed. Such thin-ning agents will be considered to be within the group designated "adjuvants". After thorough mixing in the crutcher which may take from 10 minutes to an hour, the crutcher slurry is pumped to a conventional spray drying tower, either con-current or countercurrent, in which it is dried by heated drying air at a temperature in the range of 200 to 500C.
preferably 200 to 350C. if the mix contains polyacetal carboxylate, to produce globular spray dried particles of ~ sizes in the range of No's. 8 to 100 sieves, U.S. Sieve ; SeriesO Such base beads are desirably porous, so as to be capable of absorbing nonionic detergent, and such porosity is due at least in part to the decomposition of bicarbonate to carbonate during spray drying, which produces "puffing" carbon dioxide. Normally, from 20 to 80% of the bicarbonate converts to carbonate, depending on spray tower conditions.
~ he porous base beads resulting are introduced into a suitable batch or continuous mixer or blender, such as an inclined rotary drum (batch), in which they are post sprayed at a suitable temperature at which the nonionic detergent is liquid, usually in the range of 45 to 60C., preferably 45 to 50C. In one embodiment of the invented process all the nonionic detergent, in liquid state and pre-ferably at elevated temperature in the described preferredrange, is sprayed onto the moving surfaces of th~ mass of base beads by means of an atomizing nozzle of conventional type, and during mixing it penetrates into the interiors of the beads, with some of nonionic detergent being near the ~Z5~1.7~(~
surface thereof. Then, without cooling to the solidification point of the detergent, the polyacetal carboxylate builder, in finely divided powdered form, as of particle sizes in the range of 200 to 400 mesh (although coarser particles as large as No. 100, U.S. Sieve Series, may also be used), is dusted onto the moving base beads, which now contain absorbed nonionic detergent. Some of the finely divided polyacetal carboxylate particles are drawn into the interstices and cavities of the beads by the still liquid nonionic detergent and others adhere to such detergent near the surfaces of the beads, and are held to the beads as the detergent is cooled to solidification. In such operation the polyacetal carboxylate which is held to the base beads inhibits the production of tacky product. At the same time, the holding of it to th~
beads prevents stratification of the product in its end use package during shipment and storage.
Various adjuvants of the types that would normally be post-added, such as enzyme powders and perfumes, may be added with the polyacetal carboxylate powder or before or 2Q after the powder addition. Usually, as with the nonionic detergent, it is preferred to spray liquid components onto the surfaces of the intermediate detergent composition particles but in some instances, as is also the case with application of the nonionic detergent in liquid state to the base beads, spraying is unnecessary and dripping of the liquid also serves to distribute it satisfactorily and to -- lq --~:25~7~C~
promote absorption of it into the porous particles. Powdered materials being added are preferably in finely divided powdered form, as described above for the polycarboxylate builder, but other particle size ranges may also be utilized (as they may be for the builder), although in such cases the results may not ~e as satisfactory. Also, instead of spraying the liquld material onto spray dried base beads for absorption, in some instances one may apply the liquid to granular (not spray dried) mixed carbonate, bicarbonate and zeolite particles, but such is not usually as satisfactory because such particles do no~ normally have the absorbing capacity of spray dried base beads and are less uniform.
Instead of having post-applied powdered polyacetal carboxylate particles adhered to liquid detergent that has been applied to base beads, in another and preferred process of this invention the builder is applied to the base beads as a dispersion of the polyacetal carboxylate in the normally solid nonionic detergent at elevated temperature and in liquid state. In such application, some of the polyacetal carboxylate builder may be dissolved in the liquid nonionic detergent but normally more of it is dispersed therein, preferably in finely divided particles, such as those small~r than 200 mesh, and preferably larger than 400 mesh. In such applications the base beads may be heated initially to a temperature like that of the liquid state detergent being applied but it has been found that although theoretically i25~7~0 such an operation would be thought to promote greater absorp-tion o~ the detergent and polyacetal carboxylate builder, in practice it is sufficient for the base beads to be at room temperature, at which satisfactory absorption and quick S cooling of the product result. The dispersion of polyacetal carboxylate builder particles in liquid state nonionic detergent is preferably ~prayed onto a moving bed of base beads but sometimes spraying is unnecessary, and mere dripping of the liquid medium onto the base beads is satis~actory, and in some instances it is enough merely to admix the base beads and the dispersion together without any concern fox the mode of application of the liquid dispersion to the base beads being required.
The temperature of the dispersion of polyacetal carboxylate particles in a nonionic detergent may be such as has been found to be suitable for use in the application process described. Normally such temperature will be in the range of 45 to 95C. but preferably, so as better to main-tain stability of the polyacetal carboxylate and to promote quicker cooling after application thereof to the base parti-cles, the temperature of application will be in the range of 45 to 60C., most preferably about 45 to 53 or 55C.
However, this depends on the solidification point of the no~ionic detergent, which will be the same as or low~r than the lowest temperature of such a range. Of cours~, with ~253L7~L0 higher melting nonionic detergents the lower limit of the range will be adjusted accordingly, usually being at least 2 and preferably at least 5 or 10 higher than the solidifica-tion point. The polyacetal car~oxylate will preferably be of particle sizes, substantially all (usually msre ~han 90~, preferably more than 95~ and more preferably more than 9~) of which are no larg~r than that which will pass through No. 200 sieve, U.S. Sieve Series (or a 200 mesh sieve).
~ow~ver, larger sized particles may be employed but generallysuch are not larger than 100 or 160 mesh. Preferably the particles will be in the 200 to 400 mesh range, e.g., 200 to 325 mesh, to promote penetrations into interstices of the base beads and to promote better holdings to the surfaces thereof.
In the dispersions mentioned, in which some of the polyacetal carboxylate may be in solution, the proportion of polyacetal carboxylate to nonionic detergent will normally be in the range of 1:20 to 3:2, preferably 1:10 to 1;1 and more preferably 1:2 to 1:1. However, such proportions may be adjusted, depending on the formula proportions of the polyacetal carboxylate and nonionic detergent desired to be in the end product. Still, normally no more than three parts of polyacetal carboxylate will be present with ~wo parts of nonio~ic detergent, and preferably such ~pper limit will be 1:1. If more polyacetal carboxylate is desired in the product formula it may be po5t-applied, as previously described, ~Z5~7~C~
after absorption of some of the polyacetal carboxylate and the liquid state nonionic detergent. While other materials, including particulate materials, such as enzymes, may be post-added, sometimes they may also be dissolved and/or dispersed in the nonionic detergent, with the polyacetal carboxylate and m~y be applied to the base beads together with such builder and detergent. Also, some or all of the zeolite, such as 2 to 20~ of the composition, may be dispersed in the nonionic detergent with the polyacetal carboxylate, and/or may be post-applied to improve flow properties of the product.
In some cases, some (sometimes all) of the poly-acetal carboxylate may be spray dried with the carbonate, bicarbonate and zeolite builders but in such instances the employment of mild conditions will be desired, with special care being taken not to allow buildup cf p~oduct on the spray tower interior walls, where the polyacetal carboxylate could be decomposed. So long as the spray tower conditions are such that the bead temperatures do not rise to a destabilizing temperature for the polyacetal carboxylate employed, spray drying is feasible but because this cannot always be assured in commercial spray drying processes, as a practical matter it is often preferable to post-apply the polyacetal carboxylate.
The product of the formulations given, produced by any of the methods described, is satisfactorily free flowing, ~2S~710 non-tacky and non-caking despite its contents of nonionic detergent and polyacetal carboxylate. The particles thereof are regular in shape, approximately the spherical, and the product is of desired bulk density (higher than the bulk density of usual spray dried products, which tends to be in the range of 0.25 to 0.4 g./ml.), normally being in the range of about 0.5 to 0.8 g./ml., such as 0.6 to 0.7 g./ml.
Thus, smaller packages may be employed, creating more avail-able supermarket shelf space and facilitating home laundry storage. The detergent compositions made are excellent de~ergents, with improved cleaning power against a variety of soils. Their detergencies are greater than that of a control detergent without the polyacetal carboxylate. Surprisingly, the detergency of the present compositions is better than that of a control, despite the fact that the proportion of nonionic detergent in the control is higher. It should be pointed out that the total proportion of builder is great~r in the "experimental" product, but ~hen too, the proportions of carbonate, bicarbonate, zeolite and silicate builders are lower.
The following ~xamples illustrate but do not limit the invention. Unless otherwise indicated all temperatures are in C. and all parts are by weight in the examples, elsewhere in the specification, and in the claims.
3L~5~L710 Component Parts Sodium carbonate (anhydrous) 13.6 Sodium bicarbonate 9.7 Sodium zeolite (Zeolite 4A, 20~ hydrate) 20.7 ~igher fatty alcohol polyethoxylate nonionic 15.9 detergent(l) Sodium polyacetal carboxylate [Builder ~] 23.1 Sodium silicate solids (Na2O:SiO2 = 1:2.4) 8.2 10 Magnesium sulfate (anhydrous) 1.17 Sodium citrate (viscosity regulating agent) 0.45 Moisture 4.0 Enzyme powder (proteolytic enzyme, 200 mesh) 1.52 Fluorescent brightener (Tinopal 5B~ Conc.) 1.32 15 Blue pigment (~ltramarine blue) 0.15 Perfume 9.19 100.O
(1) Condensation product of 6.5 moles of ethylene oxide and one mole of higher fatty alcohol of 12 - 13 carbon atoms sold as Neodol 23-6.5 by Shell Chemical Company
(2) Supplied by Monsanto Company (as Builder U), having a calculated weight average molecular weight of about 8,000, and of about 80% active polymer content.
The particulate detergent composition of the above formula is made by spray drying some of the formula, includ-ing the sodium carbonate, sodium bicarbonate and zeolite, to * Trade Mark ~25~L7~(~
produce base beads, and then post-blending with such base beads other components of the formula, including the nonionic detergent, polyacetal carboxylate, enzyme and perfume. The crutcher mix or slurry is made by sequentially adding to a detergent crutcher 32.5 parts of water tpreferably deionized wa.er but city w~ter of up to 150 p.p.m. CaCO3 ~quivalent may be employed), 7.9 parts of natural soda ash, 15~8 parts of industrial grade sodi~n bicarbon~te, 24.2 parts of a 20% hydrated zeolite 4A (particle size abou~ 325 mesh), 2.1 parts of MgSO4-7H2O, 0.4 part of sodium citrate, 15.6 parts of a 47.5% aqueous solution of sodium silicate of ~a2O:SiO~
ratio of about 1:2.4, 1.2 parts of fluorescent brightener (Tinopal 5BM Conc.) and 0.14 part of ultramarine blue pigment, and mixing at a temperature of about 45C. during such additions and for about 20 minutes thereafter, after which the crutcher slurry, of a solids content of about 454, is dropped to a high pressure pump which pumps it through atomizing nozzles at the top of a countercurrent spray drying tower, in which heated drying air at a temperature of about 325C. dries it to essentially globular porous particles of sizes in the No's. 10 to 100 sieves (U.S. Sieve Series) range, and of a moisture content of about 6%. In some instances a minor proportion of recycled base beads (or final product~ may be included in the crutcher mix for reworking, with appropriate modifications of the formula to allow for such.
The base beads resulting, usually at about room tempera~ure but in some cases still at a temperature between lZ~
the tower bottom air temperature and room temperature, nearer to room temperature (sometimes 5 to 30C. above it), are charged to a blending apparatus, in ~his case an inclined rotary drum, in which there are successively added 77.05 parts of the base beads, 20.72 parts of the ethoxylated alcohol nonionic detergent, 30 parts of Builder U, 1.98 parts of enzy~e and 0.25 part of perfume. The ethpxylated alcohol is sprayed onto the moving bed of base beads at an elevated temperature, 50C., at which it is in liquid state.
The Builder U and proteolytic enzyme (mixtures of amylolytic and proteolytic enzymes, e.g., 1:1 mixtures, may also be used) are "dusted" onto the moving bed of base beads after absorption thereby of the nonionic detergent (which usually occurs within about 2 to 10 minutes), after which the perfume is sprayed onto such moving intermediate product. The particulate detergent composition resulting is of particle sizes in the range of No's. 10 to 100 sieves, U.S. Sieve Series, and is of a bulk density of 0.65 g./ml. At room temperature it is free flowing, non-tacky and non-caking.
After cooling and screening, if that is desired, ~o obtain alI or substantially all of the particles in the desired No's. 10 to 100 sieve range, the product is packed, cas~d, warehoused and shipped. It is found to be of uniform compo-sition throughout the package and the contents of various packages are also uniform. It is also non-settling during shipping and storage.
A comparative product is made in the same manner as previously described except for the omission of the ~2~7~a 62301-1316 sodium polyace~alcarboxylate (Builder U) from it. Thus, instead of lO0.0 parts of product, 76.9 parts are made, and the proportions of the various components in the product are 30~ greater than those given in the above formula. When the "experimental" product is tested against the "control"
for ~etergency, in a s-tandard soil removal test which utilizes different soils deposited on a variety of substrate fabrics, the invented product is found to be significantly better in soil removal activity ~or detergency) than the control.
In the detergency tests employed an automatic washing machine containing 67 liters of water at ~9C, has charged to it four pounds oE clean clothes and three swatches each of five different test fabrics. The first and second such test fabrics are obtained from Test Fabric Company.
The first has a soil of graphite, mineral oil and thickener on nylon and the second has a soil of sebum, particulate material and kaolin on cotton. The third test fabric is cotton soiled with New Jersey clay and the Eourth fabric is a cotton-dacron blend soil~d with such a clay. The fifth test fabric, identified as EMPA lOi, is of cotton and it is soiled with a mixture of sebum soil, carbon black and-olive oil.
After washing of sets of the test fabric swatches, one set being washed in an automatic washing machine, to the wash water of which the invented composition has been charged, with the concentration thereof in the wash water being 0.07%, the wash water being of a hardness of ahout 150 p.p.m., calcium carbonate equivalent(Ca Mgratio of 3:2), and with the time for the washing portion of the cycle being about lO minutes~
'~, - ~,2s~q~
and the other set, to the wash water of which the control composition has been charged, being washed subsequently in the same machine, and after dryings, reflectances of the swatches are measured and the averages for each soiled test fabric are taken. Utilizing different factors that have been found by ex~erience to be representative of human evaluations of the importance of a detergent's cleaning powers against the various soils, the final soil removal indices are obtained for the experimental and control deter-gent compositions. The soil removal index for the inventedproduct is 26.5 points higher than that for the control, indicating a significant improvement in detergency for the invented composition.
When, in the formulation of the invented product other nonionic detergents are employed, such as Neodol 25-7, Alfonic~ 1618-65, or a suitable ethylene oxide-propylene oxide condensation product such as those marketed under the trademark Pluronic , similar improved detergency results, compared to a control from which the polyacetal carboxylate has been omitted. Also, when parts of the sodium carbonate and sodium bicarbonate are replaced by equivalent sesqui-carbonate, e.g., 10 to 50%, comparable results are obtained. -Such is also the case when other zeolites, such as X and Y, used up to 20% each of the zeolite content, are employed with th~ Zeolite 4A. This is also the situation when the silicate employed is of Na2O:SiO2 ratio of about 1:2. Changes in the adjuvants utilized, such as omission of the enzyme or replace-ment of it with amylolytic enzyme, or addition of relatively ~.2S~7~L~
small proportions of filler, such as NaCl and Na2SO4, or the presence of other builders, such as NTA or phosphates, will yield invented products also showing the described type of improvement over the control. This is also true when different polyacetal carboxylates, such as those of potassium, ammonium, lower alkyl and alkanolamine are present, of 1 to 4 carbon atoms in the alkyls thereof, when the end terminating groups employed are others than the present ones, given in the preced-ing formula, such others being those described in U.S. patent 4,144,226, and when the calculated weight average molecular weights of the polyacetal carboxylate are 5,000 or other weights within the described preferred range of 3,500 to 10,000. Of course, when the less desirable components are employed the difference in de~ergency may not be as great.
Similarly, comparable results are obtained when the manufacturing of the product is effected in other ways, under different conditions, as previously described, and utilizing components in different proportions, also as previously described. For example, when the composition of he formula is varied by changing the proportions of components ~10, +20 and +30%l while maintaining them within the ranges given, similar results are obtained. Also, when a portion of the zeolite powder, such as 2 to 20% of the detergent composi-tion is post~applied to the particles made, flowability is 2 5 improved f urther.
Ten parts of Neodol 25-7 (a condensation product of 7 moles of ethylene oxide and one mole of higher fatty - 25 ~
5~7~0 alc~hol of 12 to lB carbon atoms, on ~he average), and ten parts of Builder U, of calculated weight average molecular weight of about 8,000, are converted to a liquid ~tate dispersion-solution by first mixing them together and then hea~ing to about 93C. The builder powder, of particle sizes in the range of 325 to 400 mesh, does not dissolve in the hot nonionic detergent but disperses well therein. At an elevated tPmperature within the range of 45 to 55C., prefer-ably about 50~C., the dispersion thus made is mixed with 50 parts of base beads comprising 39% of Zeolite 4A hydrate (20% hydration), 27~ of sodium carbonate, 14% of sodium bi-carbonate, 4% of clay, 1 3~ of magnesium sulfate, 2.2% of fluorescent brightener, 0.1~ of dye, ~.6% of polymeric thickener and 11.8~ of moisture. The product resulting is free flowing, non-caking, non-tacky, non-separating, and is of excellent appearance. When tested against a ~ontrol, from which the Builder U has been omitted, it is found to be of significantly better detergency.
Similar results are obtainable when other carbonates, bicarbonates, nonionic deterg~nts and polyacstal ~arboxylates are employed, and in different proportions, within the descriptions previously given.
To improve flowability, non-tackiness and non-caking properties further, if desired, ther~ may be dusted onto the beads, after absorption of the nonionic d~tergent ~25~7~
and Builder U, about 5 parts of finely divided Zeolite 4A
or other suitable zeolite, or the zeolite, of particle sizes like those of the builder, may also be dispersed in the nonionic detergent and applied to the base beads with the nonionic and builder. If such zeolite is employed it will preferably be a Zeolite A (4A is most preferred) of particle size of 200 to 400 mesh, preferably 325 to 400 mesh (lf dispersed in nonionic detergent or post-applied) and the proportion thereof will be from 5 to 40%, preferably 10 to 20~, and the zeolite:nonionic ratio will be from 1:20 to 1:1. The ratio of the sum of zeolite and polyacetal carboxylate to nonionic detergent (in such suspension) will preferably be in the range of 1 10 to 1.1:1 or 1.2:1.
In another experiment, in which the proportion of base beads used is decreased and the dispersing tempera-ture is lower, 30 parts oP the spray dried beads are mixed, preferably by spraying of the dispersion onto a moving bed Of bead6 with 20 parts of a 1:1 dispersion of the polyacetal carboxylate in the nonionic detergent at 49C. The product is free flowing a few minutes after mixing is begun. It too is non-tacky, non-caking, non-separating, and of excellent appearance. Also, it is a better detergent than a control formula without the polyacetal carboxylate.
The procedure of Example 2 is repeated but the 25~7~
composition is made by applying the Neodol 25-7, in liquid state, at a temperature of 49C., to the moving base beads by dripping (or spraying) it thereon, after which a ~inely divided Builder U powder (200 to 400 mesh) is admixed with the intermediate product. 10 Parts of the nonionic deter-gent are mixed with 30 parts of the base beads,after which 10 parts of Builder U powder are added, with mixing.
Before addition of the Builder U the beads are "lazy"
(poorly flowing) but after addition thereof they become free flowing. They are of excellent appearance, are non-tacky, non-caking and non-segr~gating andare better in detergency than a control without the Builder U.
Variations in the formulas of Example 2 and 3 may be made, as by utilizing different nonionic detergents, s~lch as those which have been described previously, and polyacetal carboxylates of other types, previously mentioned. Variations also can be made in the base bead formulations, as have been described earlier. In all such instances, the product resulting will be satisfactory and will be of improved detergency, compared to a control from which the polyacetal carboxylate component has been omitted. In some i~stances, as when the proportion of Builder U and/or nonisnic detergent employed is sufficiently high so that flowability could desirably be improved, flow improving agents (zéolite builders can perform such function) may ~e incorporated in 5~
the final product, preferably be mixing them with the Builder U and applying the mixture thereof to the base beads, already containing deposited nonionic detergent in liquid state and at elevated temperature, or by applyir.g the flow-improving agent after a~sorption by the base beads of the nonionic detergent-polyacetal carboxylate dispersion, in th~ manner previously described. Alternatively, some zeolite, e.g., 10 to 20% of the product, may be dispersed in the nonionic detergent, too.
The mixing procedures and apparatuses may be changed too. For example, instead of mixing for twenty minutes in a batch process employing an inclined drum, mixing time may be changed to from 5 to 40 minutes, and other apparatuses may be used, such as V-blenders, fluid beds, Schugi mixers and Day mixers. The results from such changes will still be accept-able product of the desired characteristics and washing properties, with a desired bulk density being in the range of 0.6 to 0.8 g./ml., as in these working examples.
The invention has been described with respect to various illustrations and working embodiments thereof but it is to be understood that it is not limited to these because one of skill in the art, with the present specification before him or her, will be able to utilize substitutes and squivalents without departing from the invention.
The particulate detergent composition of the above formula is made by spray drying some of the formula, includ-ing the sodium carbonate, sodium bicarbonate and zeolite, to * Trade Mark ~25~L7~(~
produce base beads, and then post-blending with such base beads other components of the formula, including the nonionic detergent, polyacetal carboxylate, enzyme and perfume. The crutcher mix or slurry is made by sequentially adding to a detergent crutcher 32.5 parts of water tpreferably deionized wa.er but city w~ter of up to 150 p.p.m. CaCO3 ~quivalent may be employed), 7.9 parts of natural soda ash, 15~8 parts of industrial grade sodi~n bicarbon~te, 24.2 parts of a 20% hydrated zeolite 4A (particle size abou~ 325 mesh), 2.1 parts of MgSO4-7H2O, 0.4 part of sodium citrate, 15.6 parts of a 47.5% aqueous solution of sodium silicate of ~a2O:SiO~
ratio of about 1:2.4, 1.2 parts of fluorescent brightener (Tinopal 5BM Conc.) and 0.14 part of ultramarine blue pigment, and mixing at a temperature of about 45C. during such additions and for about 20 minutes thereafter, after which the crutcher slurry, of a solids content of about 454, is dropped to a high pressure pump which pumps it through atomizing nozzles at the top of a countercurrent spray drying tower, in which heated drying air at a temperature of about 325C. dries it to essentially globular porous particles of sizes in the No's. 10 to 100 sieves (U.S. Sieve Series) range, and of a moisture content of about 6%. In some instances a minor proportion of recycled base beads (or final product~ may be included in the crutcher mix for reworking, with appropriate modifications of the formula to allow for such.
The base beads resulting, usually at about room tempera~ure but in some cases still at a temperature between lZ~
the tower bottom air temperature and room temperature, nearer to room temperature (sometimes 5 to 30C. above it), are charged to a blending apparatus, in ~his case an inclined rotary drum, in which there are successively added 77.05 parts of the base beads, 20.72 parts of the ethoxylated alcohol nonionic detergent, 30 parts of Builder U, 1.98 parts of enzy~e and 0.25 part of perfume. The ethpxylated alcohol is sprayed onto the moving bed of base beads at an elevated temperature, 50C., at which it is in liquid state.
The Builder U and proteolytic enzyme (mixtures of amylolytic and proteolytic enzymes, e.g., 1:1 mixtures, may also be used) are "dusted" onto the moving bed of base beads after absorption thereby of the nonionic detergent (which usually occurs within about 2 to 10 minutes), after which the perfume is sprayed onto such moving intermediate product. The particulate detergent composition resulting is of particle sizes in the range of No's. 10 to 100 sieves, U.S. Sieve Series, and is of a bulk density of 0.65 g./ml. At room temperature it is free flowing, non-tacky and non-caking.
After cooling and screening, if that is desired, ~o obtain alI or substantially all of the particles in the desired No's. 10 to 100 sieve range, the product is packed, cas~d, warehoused and shipped. It is found to be of uniform compo-sition throughout the package and the contents of various packages are also uniform. It is also non-settling during shipping and storage.
A comparative product is made in the same manner as previously described except for the omission of the ~2~7~a 62301-1316 sodium polyace~alcarboxylate (Builder U) from it. Thus, instead of lO0.0 parts of product, 76.9 parts are made, and the proportions of the various components in the product are 30~ greater than those given in the above formula. When the "experimental" product is tested against the "control"
for ~etergency, in a s-tandard soil removal test which utilizes different soils deposited on a variety of substrate fabrics, the invented product is found to be significantly better in soil removal activity ~or detergency) than the control.
In the detergency tests employed an automatic washing machine containing 67 liters of water at ~9C, has charged to it four pounds oE clean clothes and three swatches each of five different test fabrics. The first and second such test fabrics are obtained from Test Fabric Company.
The first has a soil of graphite, mineral oil and thickener on nylon and the second has a soil of sebum, particulate material and kaolin on cotton. The third test fabric is cotton soiled with New Jersey clay and the Eourth fabric is a cotton-dacron blend soil~d with such a clay. The fifth test fabric, identified as EMPA lOi, is of cotton and it is soiled with a mixture of sebum soil, carbon black and-olive oil.
After washing of sets of the test fabric swatches, one set being washed in an automatic washing machine, to the wash water of which the invented composition has been charged, with the concentration thereof in the wash water being 0.07%, the wash water being of a hardness of ahout 150 p.p.m., calcium carbonate equivalent(Ca Mgratio of 3:2), and with the time for the washing portion of the cycle being about lO minutes~
'~, - ~,2s~q~
and the other set, to the wash water of which the control composition has been charged, being washed subsequently in the same machine, and after dryings, reflectances of the swatches are measured and the averages for each soiled test fabric are taken. Utilizing different factors that have been found by ex~erience to be representative of human evaluations of the importance of a detergent's cleaning powers against the various soils, the final soil removal indices are obtained for the experimental and control deter-gent compositions. The soil removal index for the inventedproduct is 26.5 points higher than that for the control, indicating a significant improvement in detergency for the invented composition.
When, in the formulation of the invented product other nonionic detergents are employed, such as Neodol 25-7, Alfonic~ 1618-65, or a suitable ethylene oxide-propylene oxide condensation product such as those marketed under the trademark Pluronic , similar improved detergency results, compared to a control from which the polyacetal carboxylate has been omitted. Also, when parts of the sodium carbonate and sodium bicarbonate are replaced by equivalent sesqui-carbonate, e.g., 10 to 50%, comparable results are obtained. -Such is also the case when other zeolites, such as X and Y, used up to 20% each of the zeolite content, are employed with th~ Zeolite 4A. This is also the situation when the silicate employed is of Na2O:SiO2 ratio of about 1:2. Changes in the adjuvants utilized, such as omission of the enzyme or replace-ment of it with amylolytic enzyme, or addition of relatively ~.2S~7~L~
small proportions of filler, such as NaCl and Na2SO4, or the presence of other builders, such as NTA or phosphates, will yield invented products also showing the described type of improvement over the control. This is also true when different polyacetal carboxylates, such as those of potassium, ammonium, lower alkyl and alkanolamine are present, of 1 to 4 carbon atoms in the alkyls thereof, when the end terminating groups employed are others than the present ones, given in the preced-ing formula, such others being those described in U.S. patent 4,144,226, and when the calculated weight average molecular weights of the polyacetal carboxylate are 5,000 or other weights within the described preferred range of 3,500 to 10,000. Of course, when the less desirable components are employed the difference in de~ergency may not be as great.
Similarly, comparable results are obtained when the manufacturing of the product is effected in other ways, under different conditions, as previously described, and utilizing components in different proportions, also as previously described. For example, when the composition of he formula is varied by changing the proportions of components ~10, +20 and +30%l while maintaining them within the ranges given, similar results are obtained. Also, when a portion of the zeolite powder, such as 2 to 20% of the detergent composi-tion is post~applied to the particles made, flowability is 2 5 improved f urther.
Ten parts of Neodol 25-7 (a condensation product of 7 moles of ethylene oxide and one mole of higher fatty - 25 ~
5~7~0 alc~hol of 12 to lB carbon atoms, on ~he average), and ten parts of Builder U, of calculated weight average molecular weight of about 8,000, are converted to a liquid ~tate dispersion-solution by first mixing them together and then hea~ing to about 93C. The builder powder, of particle sizes in the range of 325 to 400 mesh, does not dissolve in the hot nonionic detergent but disperses well therein. At an elevated tPmperature within the range of 45 to 55C., prefer-ably about 50~C., the dispersion thus made is mixed with 50 parts of base beads comprising 39% of Zeolite 4A hydrate (20% hydration), 27~ of sodium carbonate, 14% of sodium bi-carbonate, 4% of clay, 1 3~ of magnesium sulfate, 2.2% of fluorescent brightener, 0.1~ of dye, ~.6% of polymeric thickener and 11.8~ of moisture. The product resulting is free flowing, non-caking, non-tacky, non-separating, and is of excellent appearance. When tested against a ~ontrol, from which the Builder U has been omitted, it is found to be of significantly better detergency.
Similar results are obtainable when other carbonates, bicarbonates, nonionic deterg~nts and polyacstal ~arboxylates are employed, and in different proportions, within the descriptions previously given.
To improve flowability, non-tackiness and non-caking properties further, if desired, ther~ may be dusted onto the beads, after absorption of the nonionic d~tergent ~25~7~
and Builder U, about 5 parts of finely divided Zeolite 4A
or other suitable zeolite, or the zeolite, of particle sizes like those of the builder, may also be dispersed in the nonionic detergent and applied to the base beads with the nonionic and builder. If such zeolite is employed it will preferably be a Zeolite A (4A is most preferred) of particle size of 200 to 400 mesh, preferably 325 to 400 mesh (lf dispersed in nonionic detergent or post-applied) and the proportion thereof will be from 5 to 40%, preferably 10 to 20~, and the zeolite:nonionic ratio will be from 1:20 to 1:1. The ratio of the sum of zeolite and polyacetal carboxylate to nonionic detergent (in such suspension) will preferably be in the range of 1 10 to 1.1:1 or 1.2:1.
In another experiment, in which the proportion of base beads used is decreased and the dispersing tempera-ture is lower, 30 parts oP the spray dried beads are mixed, preferably by spraying of the dispersion onto a moving bed Of bead6 with 20 parts of a 1:1 dispersion of the polyacetal carboxylate in the nonionic detergent at 49C. The product is free flowing a few minutes after mixing is begun. It too is non-tacky, non-caking, non-separating, and of excellent appearance. Also, it is a better detergent than a control formula without the polyacetal carboxylate.
The procedure of Example 2 is repeated but the 25~7~
composition is made by applying the Neodol 25-7, in liquid state, at a temperature of 49C., to the moving base beads by dripping (or spraying) it thereon, after which a ~inely divided Builder U powder (200 to 400 mesh) is admixed with the intermediate product. 10 Parts of the nonionic deter-gent are mixed with 30 parts of the base beads,after which 10 parts of Builder U powder are added, with mixing.
Before addition of the Builder U the beads are "lazy"
(poorly flowing) but after addition thereof they become free flowing. They are of excellent appearance, are non-tacky, non-caking and non-segr~gating andare better in detergency than a control without the Builder U.
Variations in the formulas of Example 2 and 3 may be made, as by utilizing different nonionic detergents, s~lch as those which have been described previously, and polyacetal carboxylates of other types, previously mentioned. Variations also can be made in the base bead formulations, as have been described earlier. In all such instances, the product resulting will be satisfactory and will be of improved detergency, compared to a control from which the polyacetal carboxylate component has been omitted. In some i~stances, as when the proportion of Builder U and/or nonisnic detergent employed is sufficiently high so that flowability could desirably be improved, flow improving agents (zéolite builders can perform such function) may ~e incorporated in 5~
the final product, preferably be mixing them with the Builder U and applying the mixture thereof to the base beads, already containing deposited nonionic detergent in liquid state and at elevated temperature, or by applyir.g the flow-improving agent after a~sorption by the base beads of the nonionic detergent-polyacetal carboxylate dispersion, in th~ manner previously described. Alternatively, some zeolite, e.g., 10 to 20% of the product, may be dispersed in the nonionic detergent, too.
The mixing procedures and apparatuses may be changed too. For example, instead of mixing for twenty minutes in a batch process employing an inclined drum, mixing time may be changed to from 5 to 40 minutes, and other apparatuses may be used, such as V-blenders, fluid beds, Schugi mixers and Day mixers. The results from such changes will still be accept-able product of the desired characteristics and washing properties, with a desired bulk density being in the range of 0.6 to 0.8 g./ml., as in these working examples.
The invention has been described with respect to various illustrations and working embodiments thereof but it is to be understood that it is not limited to these because one of skill in the art, with the present specification before him or her, will be able to utilize substitutes and squivalents without departing from the invention.
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A particulate built nonionic synthetic organic detergent composition which comprises 5 to 35% of nonionic synthetic organic detergent which is a condensation product of ethylene oxide and higher fatty alcohol, and 30 to 95% of a combination of building polyacetal carboxylate of a calculated weight average molecular weight in the range of 3,500 to 10,000, alkali metal carbonate, alkali metal bicarbonate and zeolite, which zeolite is Zeolite A, X or Y, with the ratio of polyacetal carboxylate to the combination of alkali metal carbonate, alkali metal bicarbonate and zeolite being in the range of 1:5 to 2:1, the ratio of alkali metal carbonate to alkali metal bicarbonate being in the range of 1:2 to 4:1, and the ratio of zeolite to the combination of alkali metal carbonate and alkali metal bicarbonate being in the range of 1:3 to 3:1, and with the balance of the composition, if any being filler, adjuvant, moisture or other builders.
2. A substantially phosphate-free detergent composition according to claim 1 wherein the alkali metal carbonate is sodium carbonate and the alkali metal bicarbonate is sodium bicarbonate.
3. A phosphate free detergent composition according to claim 1 wherein the nonionic detergent is a condensation product of 3 to 20 moles of ethylene oxide and a mole of fatty alcohol of 10 to 18 carbon atoms, the polyacetal carboxylate builder is of a calculated weight average molecular weight in the range of 5,000 to 9,000, the zeolite is a Type A Zeolite and the proportions of components are 10 to 30% of nonionic detergent, 10 to 40% of a polyacetal carboxylate, 5 to 25% of sodium carbonate, 3 to 20% of sodium bicarbonate, and 8 to 35% of zeolite.
4. A detergent composition according to claim 3 wherein the nonionic detergent is a condensation product of 3 to 12 moles of ethylene oxide and a mole of fatty alcohol averaging 12 to 15 carbon atoms, the polyacetal carboxylate is one wherein the carboxylate is sodium carboxylate, the zeolite is hydrated Zeolite A and the proportions of components are from 10 to 20%
of nonionic detergent, 10 to 25% of polyacetal carboxylate, 10 to 20% of sodium carbonate, 5 to 15% of sodium bicarbonate and 10 to 25% of zeolite.
of nonionic detergent, 10 to 25% of polyacetal carboxylate, 10 to 20% of sodium carbonate, 5 to 15% of sodium bicarbonate and 10 to 25% of zeolite.
5. A detergent composition according to claim 4 wherein the nonionic detergent is a condensation production of 6 to 8 moles of ethylene oxide per mole of higher fatty alcohol, the polyacetal carboxylate is of a calculated weight average mole-cular weight of about 8,000, the zeolite is Zeolite 4A and the proportions of components are about 16% of nonionic detergent, about 22% of polyacetal carboxylate, about 14% of sodium carbon-ate , about 10% of sodium bicarbonate, about 21% of Zeolite 4A
of about 20% water content, about 8% of sodium silicate of Na2O:
SiO2 ratio of about 1:2.4, and 4% of moisture and about 5% of adjuvants.
of about 20% water content, about 8% of sodium silicate of Na2O:
SiO2 ratio of about 1:2.4, and 4% of moisture and about 5% of adjuvants.
6. A detergent composition according to claim 1 comprising zeolite builder in spray dried base beads containing carbonate and bicarbonate builders, and post-applied to such beads plus nonionic detergent and polyacetal carboxylate.
7. A detergent composition according to claim 4 compris-ing zeolite builder in spray dried base beads containing carbon-ate and bicarbonate builders, and from 2 to 20% of the composit-ion of zeolite which is post-applied to such beads plus nonionic detergent and polyacetal carboxylate.
8. A process for manufacturing a detergent composition according to claim 1 which comprises spray drying an aqueous crutcher mix of alkali metal carbonate alkali metal bicarbonate and zeolite, mixing the spray dried beads resulting with the nonionic detergent in liquid form at elevated temperature, where-by the detergent is absorbed into the spray dried carbonate-bicarbonate-zeolite beads, and mixing such beads containing the nonionic detergent with the polyacetal carboxylate builder, whereby said builder is held to such beads and a free flowing particulate detergent composition results.
9. A process according to claim 8 wherein zeolite powder is mixed with the product of such claim so as further to improve the flowability thereof.
10. A process for manufacturing a detergent composition according to claim 1 which comprises dissolving and/or dispers-ing the polyacetal carboxylate builder in the nonionic detergent in liquid form at elevated temperature, spray during an aqueous crutcher mix of alkali metal carbonate, alkali metal bicarbonate and zeolite, and applying to the spray dried beads resulting the polyacetal carboxylate builder-nonionic detergent solution or dispersion, with mixing, whereby such solution or dispersion is sorbed by the carbonate-bicarbonate-zeolite beads, producing a free flowing particulate detergent composition.
11. A process according to claim 10 wherein zeolite powder is mixed with the product of such claim so as further to improve the flowability thereof.
12. A process according to claim 10 wherein finely divided zeolite particles are dispersed in the nonionic detergent with the polyacetal carboxylate builder and are applied to the spray dried beads with such detergent and builder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61646284A | 1984-06-01 | 1984-06-01 | |
| US616,462 | 1984-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251710A true CA1251710A (en) | 1989-03-28 |
Family
ID=24469570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000482675A Expired CA1251710A (en) | 1984-06-01 | 1985-05-29 | Particulate built nonionic synthetic organic detergent composition |
Country Status (24)
| Country | Link |
|---|---|
| JP (1) | JPS60262898A (en) |
| KR (1) | KR860000371A (en) |
| AT (1) | ATA160885A (en) |
| AU (1) | AU581436B2 (en) |
| BE (1) | BE902551A (en) |
| CA (1) | CA1251710A (en) |
| CH (1) | CH666694A5 (en) |
| DE (1) | DE3517458A1 (en) |
| DK (1) | DK245685A (en) |
| ES (2) | ES8703925A1 (en) |
| FI (1) | FI852193L (en) |
| FR (1) | FR2565243B1 (en) |
| GB (1) | GB2159532B (en) |
| GR (1) | GR851339B (en) |
| IT (1) | IT1182248B (en) |
| LU (1) | LU85925A1 (en) |
| MX (1) | MX162808A (en) |
| NL (1) | NL8501572A (en) |
| NO (1) | NO852161L (en) |
| NZ (1) | NZ212188A (en) |
| PH (1) | PH21739A (en) |
| PT (1) | PT80556B (en) |
| SE (1) | SE8502146L (en) |
| ZA (1) | ZA853490B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE8502149L (en) * | 1984-06-01 | 1985-12-02 | Colgate Palmolive Co | ENHANCED SYNTHETIC DETERGENT COMPOSITION |
| AU744708B2 (en) | 1999-06-14 | 2002-02-28 | Kao Corporation | Granules for carrying surfactant and method for producing the same |
| KR20010044944A (en) * | 1999-11-01 | 2001-06-05 | 이강헌 | Instant seasoning rice bar manufacture method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146495A (en) * | 1977-08-22 | 1979-03-27 | Monsanto Company | Detergent compositions comprising polyacetal carboxylates |
| US4315092A (en) * | 1977-08-22 | 1982-02-09 | Monsanto Company | Polyacetal carboxylates |
| US4144226A (en) * | 1977-08-22 | 1979-03-13 | Monsanto Company | Polymeric acetal carboxylates |
| EP0015024A1 (en) * | 1979-02-16 | 1980-09-03 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing binary builder system |
| EP0021491A1 (en) * | 1979-06-18 | 1981-01-07 | THE PROCTER & GAMBLE COMPANY | Detergent containing nonionic/cationic surfactant and builder mixture |
| GR79172B (en) * | 1983-01-28 | 1984-10-02 | Procter & Gamble | |
| EG16786A (en) * | 1984-03-23 | 1991-08-30 | Clorox Co | Low-temperature effective composition and delivery systems therefor |
-
1985
- 1985-05-03 SE SE8502146A patent/SE8502146L/en not_active Application Discontinuation
- 1985-05-08 ZA ZA853490A patent/ZA853490B/en unknown
- 1985-05-14 DE DE19853517458 patent/DE3517458A1/en not_active Withdrawn
- 1985-05-15 MX MX205308A patent/MX162808A/en unknown
- 1985-05-22 FR FR8507726A patent/FR2565243B1/en not_active Expired
- 1985-05-23 NZ NZ212188A patent/NZ212188A/en unknown
- 1985-05-24 AU AU42844/85A patent/AU581436B2/en not_active Ceased
- 1985-05-24 KR KR1019850003593A patent/KR860000371A/en not_active Application Discontinuation
- 1985-05-29 CH CH2273/85A patent/CH666694A5/en not_active IP Right Cessation
- 1985-05-29 CA CA000482675A patent/CA1251710A/en not_active Expired
- 1985-05-29 AT AT1608/85A patent/ATA160885A/en not_active IP Right Cessation
- 1985-05-30 PT PT80556A patent/PT80556B/en unknown
- 1985-05-30 NO NO852161A patent/NO852161L/en unknown
- 1985-05-30 PH PH32341A patent/PH21739A/en unknown
- 1985-05-30 GR GR851339A patent/GR851339B/el unknown
- 1985-05-31 DK DK245685A patent/DK245685A/en not_active Application Discontinuation
- 1985-05-31 LU LU85925A patent/LU85925A1/en unknown
- 1985-05-31 NL NL8501572A patent/NL8501572A/en not_active Application Discontinuation
- 1985-05-31 JP JP60118697A patent/JPS60262898A/en active Pending
- 1985-05-31 BE BE0/215105A patent/BE902551A/en not_active IP Right Cessation
- 1985-05-31 ES ES543723A patent/ES8703925A1/en not_active Expired
- 1985-05-31 FI FI852193A patent/FI852193L/en not_active Application Discontinuation
- 1985-05-31 IT IT48151/85A patent/IT1182248B/en active
- 1985-06-03 GB GB08513933A patent/GB2159532B/en not_active Expired
-
1986
- 1986-05-16 ES ES555057A patent/ES8707292A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA160885A (en) | 1991-10-15 |
| FR2565243A1 (en) | 1985-12-06 |
| FR2565243B1 (en) | 1987-07-17 |
| ES8707292A1 (en) | 1987-07-16 |
| NL8501572A (en) | 1986-01-02 |
| NO852161L (en) | 1985-12-02 |
| NZ212188A (en) | 1988-05-30 |
| GB8513933D0 (en) | 1985-07-03 |
| IT8548151A0 (en) | 1985-05-31 |
| BE902551A (en) | 1985-12-02 |
| GB2159532A (en) | 1985-12-04 |
| FI852193A0 (en) | 1985-05-31 |
| CH666694A5 (en) | 1988-08-15 |
| MX162808A (en) | 1991-06-26 |
| PH21739A (en) | 1988-02-10 |
| GB2159532B (en) | 1988-04-13 |
| PT80556B (en) | 1986-12-15 |
| DK245685A (en) | 1985-12-02 |
| ES8703925A1 (en) | 1987-03-01 |
| ZA853490B (en) | 1986-12-30 |
| DK245685D0 (en) | 1985-05-31 |
| KR860000371A (en) | 1986-01-28 |
| PT80556A (en) | 1985-06-01 |
| AU581436B2 (en) | 1989-02-23 |
| ES543723A0 (en) | 1987-03-01 |
| GR851339B (en) | 1985-11-25 |
| SE8502146D0 (en) | 1985-05-03 |
| DE3517458A1 (en) | 1985-12-05 |
| IT1182248B (en) | 1987-09-30 |
| LU85925A1 (en) | 1986-02-18 |
| AU4284485A (en) | 1985-12-05 |
| ES555057A0 (en) | 1987-07-16 |
| JPS60262898A (en) | 1985-12-26 |
| FI852193L (en) | 1985-12-02 |
| SE8502146L (en) | 1985-12-02 |
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