CA1102203A - Solid detergent spotter - Google Patents

Abstract

SOLID DETERGENT SPOTTER

ABSTRACT OF THE DISCLOSURE

A composition for making a water soluble, soft spreadable solid, preferably transparent, detergent article such as a spotting stick comprising a soap component, a synthetic detergent component, an organic non-volatile, high boiling solvent component containing both water soluble and insoluble solvents and water; detergent articles containing such compositions, and methods of making such compositions and articles.

Description

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This invention relates to an improved detergen~
composition, and more particularly to a composition adaptable to forming into a water soluble, soft spreadable, form-stable, solid, optionally transparent detergent article, to the articles made ~rom such composition, and to methods for making such com-position and articles.
Transparent soaps, and methods ~or their manu~acture, l~ave been well known and available for a great many years. Being more costly to manufacture, they have been generally regarded as lu~ury items, and their transparent propertics have been equated ~ith hlgh purity and neutrality. Such products have been used almost exclusively in the toilet articles area i.e. bathing, hand and face washing, etc. However, in common with opaque soaps, they are not entirely satisfactory, particularly with respect to their cleansing efficiency in hard water, and/or with respect to some of the synthetic fibrous materials, and/or ease of manufacture, etc.
In United States Patent 3,562,167, there is disclosed a composition said to be adaptable for forming transparent de-tergent ~ars and cakes useful in hard water. ~Such composition, bars and cakes and the methods disclosed for their preparation, have been found to be subject to a number of disadvantages. More part~cularly, the products are highly hygroscopic whereby the re-sulting bars and cakes readily absorb moisture from the atmosphere,especially under conditions of high relative humidity, become sticky, and lose their ~ransparency. Stickiness is, of course, as in ~eneral, .

X

~LQZ2q3 3 objectionable in the composltion.s o~ the present invention.
Further the products are inferior ln water solubllity, deter-gency and stain removal which are of course important properties in a detergent, particularly a detergent spotting stick.
Detergent spotting sticks are likewise known in the art, ~ut are slmilarly subject to a number o disadvantages.
Thus, United States Patent 3,417,023 discloses a spotting stick prepared from a composition containing volatile solvents which tend to rapidly evaporate from the detergent stick to eventually leave a hard shrunken product incapable of being spread locally on soiled fibrous or other material unless first moistened with wate~.
~urther the resulting detergen~ stick is insufficiently water soluble, especially in hard water, and insufficiently effective for cleaning certain types of synthetic fibrous materials, soil and water insoluble stains such as ballpoint ink, motor oil, body oils, lipstick, and/or shoe polish and the like. Still further, this patent does not contemplate products which are transparent.
United States Patent 3,664,962 discloses a stain removing stick but similarly does not contemplate products which are trans-parent. It also requires the exclusive use of higher molecular weight, high melting sodium stearate soap and employs too low pro-portion of synthetic detergent and polyhydric alcohol, which has been found to result in deficiencies in cleaning-performance.
It ls an object of this inventlon to provide compositions, shaped detergent articles, and methods for their preparation which - ~a~33 will not be subject to cne or more of the above disadvantages.
Another object of this invention i.s the provision o-f an improved composition adaptable to forming into a water soluble, soft, spreadable, but form-stable solid, shaped detergent article such as a stick, especially ~:
useful as a pre-wash spotter.
Still another object of this invention is the provision of such an article which is transparent.
Yet another object of this invention is the provision of a method for making such compositions which avoids the necessity of dissolving a fatty acid soap in hot organic solvent. .
A further object of the invention is the provision of detergent composition and so~t, spreadable but form-stable, solid, shaped detergent articles which have improved cleaning effects on many different types of soils and stains and of many differen~ types of surfaces, especially artificial such as fabrics or which can be adjusted for improved efective-ness in cleaning particular types of solid, stains and surfaces.
Other objects and advantages will appear as the description proceeds.
According to the present invention; there is provided a detergent composition comprising 1. a matrix of (A) soap, (B) synthetic detergent, and (C) solvent component;
the soap component (A) constitutlng from 2 to 25% by wcight of the matrix, comprising an alkali metal, alkaline earth.metal, ammonium or amine salt of a C6 30 fatty acids said soap component providing in the matrix not more than about 14% of salts fatty acid of more than 18 carbon atoms and not more than 20% of salts of C18 or greater fatty acids and with the further proviso that ..
when potassium soap is present the total soap may be increased to twice the amount of soap used in.the potassium salt form and wherein the soap has a weighted average carbon content of at least Cl~; the synthetic dete~gent component (~) constituting from 5 ~o 88% by weight of the matrix and comprising at least one water soluble number of the group consisting of anionic organic sulfonates, anionic alcohol sulfates, anionic ether sulfates, : - 3 -B

Z~2B3 anionic ether phosphates and nonionic aliphatic detergents but a maximum of about 50% when said synthetic detergent component ~s) consists essentially only of anionic organic sulfonates or anionic alcohol sulfates or mixtures thereof, and the solvent component (C) constituting from 10 to 70% by weight of the matrix and comprising a normally liquid, substantially non-volatile organic solvent having a boiling point of at least about 100C, at least 10% thereof being water insoluble and providing at least 10% thereof in solvent compound C, said non-volatile solvent including not more than about 90% thereof of a water soluble solvent including sufficient dihydric alcohol to provide 10% and in the non-volatile component when water soluble component is present; II. a water component (D) constituting from 1 to 35 parts per 100 parts of said matrix 1, said matrix and water component being adapted to yield water soluble9 soft, spreadable, form stable9 solid, shaped detergent arti.cles.
In another aspect, the invention provides a method o preparing a composition as defined above comprising melting the free fatty acids contained in component A, mixing the molten fatty acids with component C to produce a homogeneous liquid, and admixing therein, at a temperature above the melting point of said free fatty acids and in the presence of component B and D, suf-ficient alkali metal-, ammonium-, or amine-salt forming bases to neutralize said fatty acids whereby to form their alkali metal, ammonium or amine salts ill situ.
Furthermore the invention provides a method for preparing a composi-tion as defined above comprising melting the free fatty aclds contained in component A, mixing the molten fatty acids with component C and any non-heat sensitive B components at a temperature above the solidification point of the mixture, admixing herein, at said temperature and in the presence of cornponent D, sufficient alkali metal-, ammonium-9 or amine~salt forming base to neutralize said fatty acids whereby to form their alkali metal, ammonium, or amine salts in situ, cooling the resulting liquid to just above the solidification point of said salts, and then admixing therein any heat-sensitive B components.
The matrix compositions of this invention are set ~or~h in ~,

2~3 F~gure 1 wherein the area bounded by lines connecting points A, B, C and D represents such compositions and the area bounded by lines connecting points E, F, G and H represents pre~erred matrix compositions.
Such attainment is also made possible by another feature of this invention which includes the provision of a method for preparing the above-defined composition by melting the free fatty acids contained in component A, mixing the molten fatty acids with component C to produce a homogene-lQ ous liquid, and admixing therein, at a temperature above the melting point of said free fatty acids and in the presence of components B and D, sufficient alkali metal-, alkaline earth metal-, ammonium-or amine-salt forming bases to saponify and neutralize said fatty acids whereby to form their alkali metal, alkaline earth metal, ammonium or amine salts in sltu.
The compositions of this invention are preferably shaped, generally ~y pouring the molten composition into a removabl~ mold or the package or container in which it is to ~e dispensed and~or used and parmitting the composition to 2Q cool and solidify therein, in the form of a stick of any desired size and cross-sectional configuration, e.g. circular, oval, square, rectangular, triangular, hexagonal, etc. Any other shape may however, be produced which may be particularly X

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convenient for an intended use. For example, it may be unsymmetrical or symmetrical, spherical, cuhed, egg-shaped, disc-shaped with perimeter o any desired conflguration etc. Accordingly, as em-~loyed herein and in ~he appended claims, the term "stick" is intended to include the above shapes and indeed any shape of a transparent, water soluble, soft spreadable solid shaped detergent article. The term "soft" is intended to exclude articles usually regarded as hard or hard-surfaced, referring instead to a firm, solid consistency with a relatively soft surface readily trans-ferable to the locus o the soiled surface, generally textile, where-on the stick is being rubbed, i.e. spreadable. Specific parameters of and methods for determining "so-ftners" and "spreadability" will be set forth below. ~urther, since the compositions and sticks of this invention contain a significant proportion of water insoluble solvents, it will be understood that the term "water soluble" herein applled thereto means that the film or layer of such composition locally applled to the solled area of textile or the like is so readily dispersible ln the subsequently employed aqueous detergent laundry bath or system as to be effec~ively water soluble. By the 2Q term "form stable" is meant the physical state of stability of shape under ambient conditions (e.g. 0C to about 40C; relative humidity ~rom 0% to 100%~ whereby the product does not shrink, expand, de-form or 1OW to any significant degree.
In addi~ion to enabling the atkainment of the highly `:

1~

desirable ae~t~et~cappeal o~ clear, colourles-s or coloured trans-parency, the detergent sticks of this invention have improved properties with respect to water solubility, detergency, solubili~a-tion and/or loosening o~ stains, soils films and other extraneous undesired material on the sur~ace being treated, and/or stability and resistance to changes in consistency, shape, transparency, surface softness ordinarily caused by environmental conditions of heat and humidity, 1QSS of volatile components by evaporation, etc.
They are exceptionally effective as pre-wash spotters, i.e. for application to local soiled areas of the textile, plastic or other article being cleaned prior to washing the entire article in any desired aqueous hot or cool laundry detergent bath or system. They may, in fact, be useful as pre-dry cleaning spotters, particularly in view of the relatively high content of organic, water insoluble solvent they may contain.
The compositions of this invention are further especially adaptabl~ to forming into the desired sticks, being formulated to provide optimum fluidity or viscosity properties when melted prior to the stick-shaping step, and to permit the rapid solidification 2~ into stick shape considered necessary to achieve the desired trans-parenc~. The process of this invention for making such compositions is relatively more simple and expeditious, particularly in employ-ing the more solu~le lower molecular weight ~atty acids, and neutrali~ing or saponifying them in situ.
Su~ject to the limitations discussed below, the fatty ,~1 1~2~3 acids employed in making the soaps of component A herein may contain about 6 to 30 or more, preferably about 8 to 22, carbon atoms, may be of animal, vegetable, mineral or synthetic origin, and may be saturated or unsaturated, and straight, mono- or polybranched chain hydrocarbon carboxylic acids. As merely illustrati~e of such acids, there may be mentioned caproic, caprylic, capric, aluric, myristic, stearic, eicosic, oleic, elaidic, isostearic, palmitic, undecylenic, tridecylenic, pentadecylenic, 2-lower alkyl higher alkanoic ~such as 2 methyl tridecanoic, 2 methyl pentadecanoic or 2 methyl la heptadecanoic) or other saturated or unsaturated fatty acids~
Dicarboxylic acids may also be used, such as dimeri~ed linoleic acid. Other higher molecular weight acids as rosin or tall oil acids, e.g. abietic acid, may be employed.
For the attainmen* of optimum solubility, consistency of product, viscosity, melting and solidifying properties, mixtures or blends of the above and other types of fatty acids are preferably employed containing no more than about 15% of unsaturated fatty acids, no more than about 5% of fatty acids containing more than 18 carbon atoms, and pre-ferably at least about 5% but no more than a~out 70% of 18 carbon atom fatty acids, preferably stearic acid.
One preerred class of fatty acid blends may for example contain about 0-5% of C8, 0-10% o C10, 0-30% o C12, 0-20% of Cl~, 10-50%
o$ C16, and 5-70% of C~18 sa~urated fa~ty acids. Readily available c~mmercial blends, and mixtures of such blends for obtaining the most suitable dis~ribution of fatty acids, which may be employed include distilled palm and palm kernal oil fatty acids, distilled coconu~ oil atty acids, hydrogenated tallow atty acids, and commercial stearic acid. The fatty acid content, in parts by weight, of several such blends, and mixtures thereof, are illus-trated in the following table.

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Z~3 TABLE I

. _ . . . . , _ . ~ . _ _ a b c d e f g h ~ . _ _ ~
C8 ~ 4 0 - 2.0 - 2.0 1.3 2.7 ClQ - 3.0 8.6 1.5 - 1.5 1.0 2.0 C12 - 45.0 66.2 22.5 - 22.5 15.0 30.1 Cl4 3-0 19.0 25.0 11.0 - 9.5 8.3 13.7 C16 30.0 11.0 - 20.5 50~5 30.5 23.7 17.4 C18 65.0 4.0 - 34.5 43.4 23.5 44.6 24.3 ~ax.
Unsat. 2.0 12.0 - 7.0 4.0 8.0 5.0 8.7 In the above table, blend a = commercial hydrogenated tallow fatty acids b = commercial distilled coconut oil fatty acids c = commerclal synthetic fatty acids d = 1 : 1 mixture of a and b e = commercial stearic acid f = l : 1 mixture of b and e g _ 2 : 1 mixture of a and b h ~ 1 : 2 mixture of a and b For the in situ saponiication of these fatty acids according to the process of this invention there may be employed any alkali me~al-, alkaline earth metal-, ammonium-, or amine-salt orming base, as for example sodium, potassium magnesium, or ammonium hydroxides, mono-di- or triethanol-, or -propanol-amines, g _ ~' .

or any other such ~ase y~elding a water soluble salt or soap of the :Eatty acid being saponified. The base is preferably in the form of a concentrated aqueous solution or dispersion for example of a~out 20 to 49% concentration, and at a~out the temperature of the molten fatty acid when admixed therewith. An approximately stoichiometric amount of base is preferably employed unless a product is desired containing slight amounts of excess fatty acid or base, The component A soap, apart from its known detergency function~ contributes body, firmness and non-sticky proper~ies to the detergent sticks of this invention. However, the use of too high a proportion of component A in preparing the produc-ts of this invent~on may unduly raise the melting or fluldizing temperature ~to about 110C or more), the viscosity of the hot, molten fluid, and the rate of solidification thereof, thereby preventing proper operation o the stick-making process, and tends to unduly reduce the transparency and rate of dissolution o the resulting stick.
The use of too low a proportion of component A, on the other hand, unduly reduces the viscosity of the hot~ molten fluid and the rate 2~ of solidification thereof, in addition to yielding sticks which are too soft and sticky at any level (proportion~ of componen~s B and C.
The compositions and sticks of this invention may contain about 2 to 25%l preferably about 4 to less than 15%, and still more preferably about 6 to 12% of component A, of which at least about ~0%
are preferably or equivalent to the alkali metal salts of hydrogenated - 10 ~

.. . . .
: :

tallow fatty acids.
As component B there may be employed substantially any water soluble synthetic orgartic detergent, or mixtures thereof, of the cationic, amphoteric, anionic sulfonate and sulfate, or non-ionic aliphatic types, ample description of which appear in McCutcheon's l'Detergents and Emulsifiers'l, 1969 Annual, and in IlSurface Active Agentsl~ by Schwartz, Perr~ and Berch, Vol. 11, 1958 (Interscience Publishers).
Suitable cationic detergents include generally the quaternary ammonium compounds which may be desc~ibed as con-taining, in addition to the usual halide (chloride, bromide, iodide, etc.~, sulfate, phosphate, or other anion, aliphatic and/or alicyclic radicals, preferably aldyl and/or aralkyl, bonded through carbon atoms therein to the remaining 4 avail-able positions of the nitrogen atom, 2 or 3 of which radicals ~`
may be joined to form a heterocycle with the nitrogen atom9 at least one of such radicals being aliphatic with at least 8, up to 22 or more~ carbon atoms. As illustrative of such cationic detergents, there may be mentioned distearyl dimeth-yl ammonium chloride~ stearyl dimethyl ben7yl ammonium chlo~ide coconut alkyl dimethyl benzyl ammonium chloride, dicoconut alkyI dimethyl ammonium bromide, cetyl pyridinium iodide, and cetyl pyridinium iodide, and cetyl trimethyl ammonium bromide and the like.
Suitable amphoteric detergents, combining potentially anionic and cationic groups in one molecular, include the alkyl Z~3 beta-iminodipropionates and iminopropionates, and long chain imidazole derivatives. ~llus~rative examples lnclude the disodium salt of lauroyl-cycloimidinium-l-ethoxyethionic acid-2-ethionic acid, dodecyl beta-alanine, the inner salt of 2-trimethylamino lauric acid, and as ~witterionics, the subs*ituted betaines such as alkyl dimethyl aml~o acet~es-. Several ex-amples of this class of zwitterionics are disclosed in Canadian Patent 696,355.
Suitable anionic water soluble detergents include the alkyl aryl sulfonates, especially the higher (e.g. 10 to 20 or more carbon atom) alkyl benzene sulfonate salt, preferably those alkyl benzene sulfonates wherein the alkyl group contalns 10 to 16 carbon atoms~ The alkyl group is preferably linear and especially pr0ferred are those of a~erage alkyl chain lengths of a6Out 11 to 13 or 14 carbon atoms, such as the linear dodec~l benzene sul-fonate salts.
Preferably also, the alkyl benzene sulfonate has a high content of the 3-alkyl phenyl isomer and a correspondingly low content (well below 50%) of the 2- and 4- alkyl phenyl isomers. One suitable type of such detergent i5 described in United States Patent 3,320,174.
Also, typical of the useful anionic detergents are the olefin sul-2Q fonate salts. Generally the~ contain long chain alkenyl sulfonates or long chaln hydroxyalkane sulfonates ~with the OH being on a carbon atom which is not directly attached to the carbon atom bearing the -SO3 group). More usual-ly, the olefin sulfonate detergent comprises a mixture of these two types of compounds in varying amounts, often together with long chain disulfonates or sul~a~e-sulfonates. Such olefin sulfonates are described in many patents, such as United States Patents 2,061,618; 3,409,637; 3,332,880; 3,420,875;

3,428,654; 3,506,580; and British Patent 1,139,158, and in the article by Baumann et al. in Fette-Seifen-Anstrichmittel, Vol. 72, No. 4 at pages 247 -253 (197Q). As indicated in these patents and the published literature, the olefin sulfonates may ~e made from straight chain alpha-olefins, internal ole$ins~, olefins in which the unsaturation is in a vinylldene side chain ~e~g~ dimers of alpha-oleein), etc., or more usually, mlxtures of such com-pounds, wit~ the alpha-olefin usually belng the ma~or cons~ltuent. The sul-fonation is usually carried out with sulfur trioxide under low partial pres-sure, e.g. SO3 hlghly dllu~ed with inert gas such as air ni~rogen or under vacuum. Thls reactlon generally yields an alkenyl sulfonlc acid, o-ften to-gether wlth a sultone. The resultlng acldic material is generally then made alkaline and treated to open the sultone ring to form the corresponding hydroxy alkane sulfonate and/or alkenyl sulfonate. The number of carbon atoms in the olefln is usually within the range of about 10 to 25, more commonly about 12 t 20 e g a mixture of princlpally C12, C14 and C16, g a6Out 14 carbon atoms or a mixture of prlnclpally C14, C16 and C18, having an average of about 16 carbon atoms.
Another class of water soluble synthetic organic anionic detergents includes the higher ~e.g. 10 to 20 carbon atoms) paraffin sulfonates. These may be the primary paraffin sulfonates made by reacting long chain alpha-olefins with bisulfite, e.g., sodium bisulfite, or parafein sulfonates having the sulfonate groups distributed along the paraffin chain, such as the products made By reacting a long chain paraffin with sulfur dioxide and oxygen under 2Q ultraviolet light, followed by neutralization with NaOH or other suitable base ~as ~n United States Patents 2,503,280; 2,507,088; 3,260,741; 3,372,188; and German Patent 735,096). The hydrocarbon substi~uent of the paraffin sulfonate preferably contains about 13 to 17 carbon atoms and the paraffin sulfonate will normally be a monosulfonate but, i-f desired, may be a di-tri- or higher sulfonate. Typically~ a paraffin disulfonate may be employed in admixture ~ith the corresponding monosulfonate, for example, as a mixture of mono- and di-sulfonates containing up to about 30% Oe the disulfonate.
The hydrocarbon substituent of the paraffin sulfonate will usually Be linea~ But Branched chain parafin sulfonates can ~e~also employed. The paraff~n sulfonate used may be terminally sulfonated or the sulfonate subsitu-.

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ent may~be ~olned to the 2-carbon or other carbon atom of the chain. Similar-1~, any di- or higher sulfonate emplo~ed may have the sulfonate groups dis-tr~uted ~ver different carbons of the hydrocar~on chain.
Additlonal ~ater soluble anlonic detergents include the higher acyl sarcosinates ~e.g~, sodium lauroyl sarcosinate) the acyl esters, e g., oleic acid ester, of isethionates and ac~l N-met~yl taurldes, e.g. potassium N-methyl lauroyl- or oleyl taurides. Another type of anionic detergent is a higher alkyl phenol sulfonate, for example a higher alkyl phenol disulfonateg such as one having an alkyl group of 12 to 25 carbon atoms, preerably a linear alkyl of about 16 to 22 carbon atoms, which may be made by sulfonating the corresponding alkyl phenol to a product containing in excess of 1.6, pre-~erably above 1.8, e.g., 1.8 to 1.9 or 1.95 SO3H groups per alkyl phenol mole-cule. The disulfonate may be one whose phenolic hydroxyl grQup is blocked as by etherification or esterification; thus the H of the phenolic O~l may be re-placed by an alkyl e.g., ethyl, or hydroxyalkoxyalkyl, e.g., a -(CH2CH2O)xH
group in which x is 1 or more, such as 3, 6 or lO, and the resulting alcoholic OH may~be esteri~ied to ~orm, say a sulfate, e.g., -SO3Na.
Qther suitable anionic detergents are C8-20 alkyl sulfates such as lauryl sulf~te, tallow alcohol sulfate, and alpha- or omega-methoxy octadecyl 2Q sul~ate, and C8 18 alkanoyl mono- and diglyceride sulfates and sulfonates.
Still other suitable anionic detergents are the sulfate esters of non ionlc detergents, i.e. the reaction products of about 1 to 20 moles of a C2 ~ alkylene oxide, preferably ethylene oxide, with 1 mole of C8 24 reactive ~ydrogen-containing compound including aliphatic and alicyclic alcohols such as lauryl, tallow, oxotridecyl, coconut oil, and abietyl alcohols, aliphatic dihydric alcohols such as polyoxypropylenated ethylene and propylene glycols, diamines, and dithiols, aliphatic and alicycllc carboxyl~c aclds such as stearic acid and abietic ac-id, aliphatic mercaptans such as dodecyl mercaptan, aliphatic and alicyclic amines such as stearyl amlne and rosin amine, alipha-3Q tic amides such as stearyl amlde, and alkyl phenols such as nonyl and dinonyl , 1~2~3 phenol.
~ hile the a~orementloned structural types of organic carboxylates, sulfates and sulfonates are generally preferred, the corresponding organic carboxylates, phosphates (see e.g. United States Patent 3,595,968) and phos-phonates are also useful as anionic detergents.
Generall~, the anlonic detergents are salts of alkali metals, such as potassium and especially sodium, although salts of alkaline earth metals, ammonium cations and substituted ammonium cations derived from lower ~2 to 4 carbon atoms) alkanolamines, e.g., triethanolamine, tripropanolamine, di-ethanol monopropanolamine, and from lower ~1 to 4 carbon atoms) alkylamines, e.g., methylamine, ethylamine, sec-butylamine, dimeth~lamine, tripropylamine and triisopropylamine, may also be utilized.
Of the anionic detergents ~he alkali metal salts of sulfated and sulfonated moieties are preferred over the carboxylic, phosphoric and phos-phonic compounds.
Aliphatic nonionic detergents operative as or in component B may be described as reaction products of about 2 to 50 moles of a C2 ~ alkylene oxide, pre~erably ethylene oxide, with 1 mole of a C8 24 reactive hydrogen-containing aliphatic compound, illustrati~e of which aliphatic compounds are 2Q those reactive hydrogen-containing compounds discussad abov0 as precursors of s~l~ate esters o non ionic detergents which are aliphatic.
Preferred nonionics surfactants are those represented by the formu~ ;
la:
R ~C2H40)nH
~herein R represents the residue of a saturated straight or branched chain aliphatic alcohol, preferably a primary alkanol of about 8 to 20, preferably about 12 to 18 carbon atoms and n is an integer from about 2 to 50 preferably aBout 3 to 20.
Typical commercial non ionic surfactants suitable for use in the ~n~ention ~nclude an ethoxylation product ha~ing an average of 11 ethylene ~Z~3 oxide un~ts 9~ a 14 to 15 car~on atom chain ~atty alcohol; a 12 to 15 carbon atom chain fatty alcohol ethoxylated with an average of 7 ethylene oxide units; a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxide units and such products being variously, or substantially equivalent to the reaction products of 11 moles of ethylene oxide (E.O.) with 1 mole of a C14_15 primary alkanol or 1 mole of C12 15 primary alkanol, of 7 moles E.O. with 1 mole of a C12 15 primary alkanol, and 3 : 1 to 1 : 3 blends of the reaction product of 20 - 50 moles ~Ø with 1 mole of a C16 18 primary alkanol, and of 3 - 5 moles E.O. with 1 mole of Cg 10 alkanol.
Other su~table non ionic aliphatic detergents include the liquid and semi-solid reaction products of 3 - 20 moles E.O. with 1 mole of Cll 15 secondary alkanols, the Pluronics, and the reaction products of 5 - 7 moles E.O. with 1 mole of C16 18 alkane diols-Still other suitable aliphatic non ionic detergents are those of the polar type which can also serve to~enhance lathering and cleaning pro-perties of other types of detergents, particularly anionic detergents. In a polar type non ionic detergent, the hydrophilic group contains a semi--polar ~ond directl~ be~ween 2 atoms, e.g. N -~ O, P -~ O, As -~ O, and S -~ O, the arrow being the conventional representation of a semi-polar bond. There is ~ charge separatlon between the 2 directly bonded atoms, but the molecule bears no net charge and does not dissociate into ions. Illustratîve types are amin0 oxide~ of the formula R2R2R3N ~ O and phosphine oxides of the formula R R R P - O wherein R is C10 18 alkyl, alkenyl or alkanol and R and R are independently Cl 3 alkyl or alkanol, for example dodecyldimethyl amine and phosphine oxides.
As indicated a~ove, mixtures of the above described detergents may be employed as component B. A preferred embodiment is the use of at least afiout 40% up to 100%, of the non ionic reaction product of about 2 to 50, preferably about 5 to 15 moles o ethylene oxide with 1 mole of ethylene oxide t~th 1 mole of a saturated aliphatic alcohol, prefera~ly a primary ;22~

alkanol, of abaut 8 to 20, preferably about 11 to 16, carbon atoms, as or in component B.
T~e detergents of component B contribute lmproved hard water solubi-lity and lmproved detergenc~ to the composltlons and sticks of this invention, particularly in hard water and~or with respect to the synthetic fibrous ma-terials such as nylon, polyesters such as Dacron and polyacrylonitriles such as Orlon and Acrilan. They also increase the water solubility and rates of wetting and dlssolution o~ such compositions and sticks. This component B
should contaln little or no mineral salts, a fairly common ingredient of com-mercial detergent formulations, to minimize efects on the transparency pro-perties of the products, and may be employed in the compositions and stic~s of this invention in amounts ranging from about 5 to 88%, preferably about 25 to 76% b~ t~eight, most preferably 35 to 76%.
A ma~or portion (~ 50%) and preferably from 75 to 100% of the com-ponent C solvent should be normally liquid, i.e. with a solidification point tS.P.) below about 40C, preferably below room temperature, and a boiling po~nt of at leas~ about 100~C, preferably at leas~ about 120C, up to about 40~C. It should be substantially non-volatile9 with a negligible vapour pressure at room temperature and negligible loss by evaporation on ageing or 2Q storage. Thus, particularly good non-volatilit~ is indicated by a loss of ~eight of 5% or less after 2 hours at 105C or after 10 hrs. at ~3C for a 2~ grams sample of the solvent in a container with an evaporating surface o aaout 46.5 sq. cm. ~2.3 sq. inches) placed in an oven provided with a flow o~ alr.
Q~ the sald non-volatile fraction of said component C at least about 10% should be water insoluble ~e.g. benzyl alcohol) to provide 10%
thereo~ in component tC~ and preferabl~ at least 25% up to 100%. One or more su~stantially~water solu~le organic solvents, such as propylene glycol may constitute a part of the non-volatlle fraction ln an amount no more than about 90% preferably not more than 75%, and still more preferably not above ;~, .

~122~3 :

aBout 5Q% ~ weigh~ of said fraction. The preferred water-soluble solvent should contain a dih~dric alcohol, such as propylene glycol.
As a suitaBle substantially water insoluble organic solvent, benzyl alco~ol is preferred, or lauryl alcohol or terpineol, but as illustrative of other sucb sol~ents ~hich may be employed in or as component C, there may be mentIoned, as a rule o~ thumb, any such liquid more water insoluble than Benzyl alcohol, including generally any substantially water insoluble alipha-tic, alicyclic or aromatic liquid hydrocarbon, halogenated (iodine, bromine or preferably chlorine) hydrocarbon, hydroxylated hydrocarbon, ether, ester, or the like having the abo~e-described properties, for example octane, hexa-decane, chlorohexane, chloro- and dichloro-benzene, heptyl, Oxotridecyl and hexadecyl alcohols, abietyl alcohol, octanediol, phenethyl alcohol, mono- and di-Cl 14 alkyl phenols, phenyl ether, benzyl ether, 1,2-dibutoxy benzene, 2-benzyloxy-ethanol, butyl ether, diethyl- and dibutyl-phthalates, benzyl pro-pionate, isopropyl myristate, palmitate, and stearate, and the like. Benzyl ~lcohol is also unique (with others) in providing body and form-stability to the matrix products.
Similarly, as a rule of thumb~ the substantially water soluble solvent in or as component C may be any such solvent which is more wa~er soluBle than ~enzyl alcohol. It may be of any type chemically, but is general-ly~a mono hydric or polyhydric alcohol, ether alcohol, or amine such as 1,7-heptanediol, the mono- and poly-ethylene and -propylene glycols of up to about 4000 molecular ~eight, and the mono-Cl 14 alkyl ethers thereof, sorbitol, glycerol, glucose, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-~butanol, mono-, di- and triathanolamine, 2-amino-1-butanol, and the like, especlally the polyhydric alcohols and alkanolamines.
~s pointed out the solubility of benz~l alcohol (reported ~ g. per 10~ ml. o$ ~ater at 170C~ is~ taken as a general gulde for selecting water-soluble and ~ater-~nsQlu~le sol~ent.~. As a further guide, a solvent may be cons~dered water-insoluble if its solublllty~ in water at 20~C ls less than .

~Z~3 about ln% By~eig~t and preferabl~ less ~han about 5% by weight.
Opera~le ~atios o~ ~ater~insoluble to water-soluble solven~s will fall ~ithin t~e range of lQ:l to 1:10 preerably 10:1 to 1:5, and more pre-fera~l~ 8:1 to 1:3. Other pre~erred ratios are 5:1 ~o 1:3 and 4:1 to 1:2.
T~e solvent componen~ C is essential for the production of sticks ~hich are transparent and further functions as a coupling or mutual solvent ~or the component A soap and its att~ acid precursor, and the component B
detergent. It also fluidi~es the melt and facilitates the shaping thereof ~nto sticks Nhich solidif~ rapidly on cooling in accordance with the process o$ this invention. It further improves the surface softness and solubility of the stick products. The use of substantially all water soluble solvents in component C while good mu~ual or coupling solvents for components A and B, and good water solubilizers of the stick products, tend to unduly increase the softness, tackiness and hygroscopicity thereof, particularly those of the polyh~dric alcohol t~pe~ in storage and use. Such tendencies are con-trolled in accordance with this invention by limiting the proportions of water_ soluble solvents and employing water-insoluble solvents in component C as described above, in addition to the other functions perormed by such in-soluble solvents. ~t should however, be noted that a controlled degree o~
2a ~ygroscop~c~t~ in the products hereof ma~ be benefic~al in pre~enting such products from dry~ing out, s~rinklng and cracklng in storage and use. Com-ponent C) like component B, should of course also be stable or resistant to the action of the base or alkaline material used in making the component A
soap in situ according to the process of this invention.
Component C should generally constitute no more than about 70%, pre-~erabl~ no more than about 60%, still more preferably less than about 50%, of the composition and sticks of this invention to avoid unduly reducing the detergenc~ properties thereo~ because of the resulting lower proportions of components A and ~, and to a~oid undul~ increasing the sweating (liquids 3~ leakagel, hygroscopicit~, softness, and tackiness of the sticks. In general, ~ 6 ., -. .

Z~3 the compositions and sticks of ~his invention may contain approximately by weig~t, 10 to 70, preferably 20 to 60, and more preferably 20 to less than 50% of component C.
tVater component D contributes to a lowering of the viscosity of the present compositions in the f]uid or molten state, and facilitates neutraliza- -tlon of the fatty acid precursors of the component A soaps in the processes for making the sticks and compositions of this in~ention, in addition to assisting in solubilizing components A and B. Further, some it not all the water is conveniently introduced in the form of an aqueous solution of the base of alkaline material employed in the in situ neutralization or saponifi~
cation of the fatty acid precursors of the component A soap. Water also in-creases the water solubility and transparenc~ of the sticks of this invention and its partial loss from the sticks by evaporation during ageing and storage, particularly from the outer layers of the sticks, is balanced by, the hygro-scopic tendencies of other components, especially polyhydrîc alcohols in component C. Too low a proportion of water detrimentally affects the workabi-lity of t~e present compositions and the transparency of the resulting sticks.
TOQ high a proportion unduly reduces the rate of sol dification of these com-positions into sticks, and unduly increases the stickiness and softness there-Of-In general, the compositions and sticks of this invention should contain, approximately by weight, 1 to 25 parts, preferably 5 to 15 parts, and more preferably 5 to 10 parts, of water component D, and may further con-tain minor proportions, for example a total of from 0 up to about 5 or 10%, of common additives including colouring materials such as dyes, brighteners or optical dyes, preservatives, UV absorbers, stabilizers, perfumes, disin-fectants, foaming and lathering agents, enzymes fillers, sequestrants, soil suspending agents, anti-redeposition agents, and the like. ~illers and builders can, likewise, be added in any convenient amounts (e.g. 1 - 85%).
Sodium sulfate is a usual filler with the phosphates, carbonates, borates~

. . .
, . .. .

and ~ cates as illustrative inorganic builders. Among the la~ter, sodium tripoly phosphate is the usual choice. Organic builders such as trisodium nitrilotriacetate, hydroxyethyliminodiacetic acid, sodium salts, citrates, gluconates, and the like are useful. Polyelectrolytes, and sequestration agents can also be used in any desired amounts.
According to the process for preparing the compositions of this invention, it is preferred to melt the free fatty acids corresponding to the soaps of component A in a heated vessel, mixing in components B and C, and gently stirring the mixture at a temperature above, but preferably no more l~ than about 30C. Above more preferably about Z to 15C above the melting point of the said fatty acids (usually abou~ 70 to 80C) until a homogeneous llquid is obtained. A solution of the selected salt forming base in water component D, preferably at the temperature of said homogeneous liquid, is then mixed therein, preferably gradually and/or in small increments to avoid lumps and overheating, until the in situ neutralization and/or saponification of the fatty acids in the said liquid is complete. Desirably, an approximate-ly stoichiometric amount of the base is employed to avoid excess base or fatty acids in the product. Neutralization of the product can be ascertained for example by periodic testing with phenolphthalein indicator. If desired the 2Q detergent component B may be first dissolved in the heated solvent component C and the resulting solution filtered to remove mineral salts and any other undissolved material prior to mixing the B and C components, in the form of the resulting hot clear solution, into the molten acids.
After all the base has been added and the resulting hot liquid pro-duct mixed sufficiently until it is determined that the acids are neutralized, any desired minor amounts of the above described known additives to detergent formulations are mixed in together, if desired with any deslred additional amounts of water component D. Alternatively, some of the water component D
may be added together with detergent components B and/or solvent component C.
3a ~n some instances, it may be desirable and within the scope of this . ~ - . . . . ..

invention to replace up to about 75% or more of the lnitially melted free fatty acids by their corresponding soaps or salts, e,g. neat or kettle soap, with of course a corresponding reduction in the proportion of soap- or salt-forming base subsequently mixed with the hot melt to neutralize or saponify the free fatty acids therein.
According to another embodiment of the invention, when a product is being prepared containing a heat sensitive anionic organic sulfonate or alcohol sulfate detergent as or in component B, such detergent is not mixed with the molten fatty acids prior to the exothermic neutralization reaction lQ thereof with the base, but is instead sl~bsequently mixed into or with the previously neutrali~ed and cooled liquid ~to just above the solidificatlon point of the said liquid containing the soap or fatty acid salt component A, the solvent component C, and any remaining detergent portion of component B.
The hot melt liquid composition of the invention produced as de-scribed above may if desired be cooled and solidified in bulk or any other desired ~orm. According to a further feature of ~his invention, such cooled and solidi ied composition is remelted, or more preferably said hot liquid composition is employed wi~hout, such intermediate cooling, solidification, and remel~ing steps with attendant possible loss of components by decomposi-2Q t~on and/or evaporation, but is instead directly poured into molds, packages or containers of the desired shape, and si~e, e.g. sticks, and cooled to be-lo~ the solidification point. The improved water soluble, soft, spreadable, solid optionally transparent detergent sticks of this invention are thereby produced and may if desired be aged a short time to permit equilibrium with the environment.
The matri~ products o~ this invention provide an unique combination o~ b~th physical and chemical characteristics. As pointed out above they are generally transparent, stable, so~t, spreadable, solid form-stable materials which exhibit excellent detergency in a clothes laundering process and have 3~ have excellent solubility characteristics particularly in the washing machine.

~3~

~z~

The products of this invention generally have a soil removal ability comparable, if not superior to presently used clothes laundering detergents.
The detergency is conveniently measured ~y bo~h the standard Tergotometer tU.S. Testing Company, Hoboken, New Jersey U.S.A.) test and with practical machine washes. In the Tergotometer test an aqueous solution of detergent (.1-.5% concentration) is stirred with soiled swatches (and usually with clean s~atches as well as for redeposition effectiveness) and the detergency is then conveniently determined by ~hefore~ and "after'l readings on a Colour Differ-ence meter ~e.g. Gardner Colour Difference Meter). The test may be run at ln any temperature (generally room temperature to the boil) with stirring at from 0-250 rpm. for 5-20 minutes (conveniently 10 minutes) at water hardnesses from 0 to 300 or more ppm ~as CaC03). Prior to th0 "after" readings, the cleansed swatches are rinsed for a few minutes in the same hardness water as used in the detergency step, dried and then evaluated.
The products of this invention also are outstanding for use on various stains e.g~ grease~ oily soil, lipstick, ball point ink, etc~ The dissolution speed of the products of this invention are measured in water at from room temperature to the boil (generally and conveniently at 40C).
The method is generally to add 2 grams o~ product to 500 ml. of water at a selected temperature and stir at selected standardized condi~ions until all the product is dissolved. The procedure, specifically is to use a 600 ml beaker o~ 12 cm height and 8.5 cm in diameter (very flat bottom) graduated every 50 ml.. Place the 500 ml water in the beaker, set the temperature add 2 grams of product and stir. The stirring is effected by means of a magnetic stirrer which is a cylindrical bar having a 1 mm. plastic coating. The over-all dlmensions of the bar are 12 mm diameter and 6.2 mm in length~ The speed of rotation is adjusted to give a vortex with its apex at the 300 ml gradua-~i~n of the beaker.
The products of this invention have dissolution speeds when measured as aforedescribed of from 1/2 to 5 mins. at 40C.

:
. . . : . . .

2~3 The penetration hardness of the products of this invention can be measured by means of the ASTM Method D217-52T ~Richardson Method). Values ob~ained for the ma~rix products of thls invention vary from about 70 to about 120 (ten~hs of a millimeter).
The product stickiness ~also spreadability and transferability by rubbing) ls determined by rubbing under a 2 kg weight a molded 1" cylinder of product on a standard cotton cloth and (10 cm. long) and measuring the amount of product released by~ friction as the cloth is pulled under the weighted cylinder. Suitable products have friction values (translucent factors) of about 100 mg. to about 300 mg. of product per 10 cm. strip of cotton cloth.
Preferred products have transferability factors of from above 150 to less than 300.
The product transparency is conveniently measured ~y means of a lamp/photocell/galvanometer system, reading the percentage of transmitted light after a zero adJustment. Spectrocolorimeters can also be used. Sub-stantially total transparency (i.e. ~ 95%) can be achieved with the products of this invention.
Other relevant parameters of the products of this invention are the solidification temperature (S.P.) and viscosity of the product in the fluid state since these are important considerations in processing the instant com-positions particularly into the shaped forms hereinbefore described. These parameters have a direct effect on rate of production, siz~ and handling of such shaped forms (e.g. sticks) as well as affecting the transparency and stickiness of the final product. Generally, the S.P. of the matrix products o~ this invention range from about 40C to 100C and the viscosity, as measured by-a falling ball visometer~ may range from about 50 cps to 3000 cps with mosk suitable values in the range of about 1000-2000 cps.
The following examples are not limitative and are only illustrative of preferred embodiments of this invention. All amounts and proportions here-3a in are by weight and unless ot~erwise indicated.

, Formulation 1 Parts Hydrogenated tallow fatty acids 12.5 senzyl alcohol 20.0 Propylene glycol 30.0 *

Non ionic C14 15 alkanols ~ 11 E.O. 28.0 Formulation 11 Deionized water 5.0 Low chloride 38% aqueous NaOH 4.1 ~ormulation 111 Pigmosol slue 5G-1% aqueous solution 0.4 *Reaction product of 1 mole of C14 15 alkanols with all moles of ethylene oxide.
The ingredien~s of formulations 1 and 11 are separately heated in a mixing tank to 80-85C. with good agitation until homogeneous, and the Formula-tion 11 mixture slowly added with agitation to Formulation 1. A few drops of phenolphthalein indicator are then added to the mixture and if the mixture is still colourless, small increments of the NaOH solution are added till the mixture just turns pink. The ~ormulation 111 colour is then mixed in, and the 2Q mixture held at a~out 71C. while being poured into stick molds. The sticks are solidiied by cooling carefully and slowly to ensure transparency of the sticks.

The resulting transparent, water soluble, readily spreadable deter-gent ~ticks are highly effective for removing ball pen ink stains, cuffs and collar discolourations, etc. when the stained or soiled areas are rubbed with the sticks and then washed in an aqueous laundry detergent bath. The sticks are stable to varying environmental conditions for extended periods of time.
EXA~PLE 2 _ The procedure o Example 1 is repeated with the following formula-tions, the results being nearly equal:

: Formulation 1 Parts Hydrogenated tallow fatty acids10.00 Benzyl alcohol 28.65 Propylene glycol 28.65 ' C14_15 lkanols 11 E.O. 28.00 r' Formulation 11 Deionized water 4.50 35% aqueous NaOH 4.40 Pormulation 111 Pigmasol Blue 5G - 1% aqueous solution 0.10 ` optiblanc BTll* 0.10 optiblanc 2MG* 0.10 *6% solution of each optical brightener, freed of mineral salts, . in 1:1 benzyl alcohol: propylene glycol.

Examples 1 and 2 are repea~ed except that the nonionic detergen~
~n Formulation 1 is replaced by an equal amount of the following detergen~s:
~A) Cationic distearyl dime~hyl ammonium chloride (B) 1:1 mixture of ~A) and C14 15 alkanols + 11 E.O
2~ tc) Anionic sodium C14 17 paraffin sulfonate (100% active, pure, desalted)*
tD) 1:1 mixture of (C) and C14 15 alkanols + 11 E.O.
*Added as a 66.5% solution in 1:1 benzyl alcohol: prop~lene glycol.
The results are similar to those of Examples 1 and 2. When (C) is employed, it may alternatively be included iTl ~ormulation 111 instead of 1.
In the ollowing examples set forth in table 11 the parts of in-gredients are set and the identiication thereo~ given in table 1. The pro-cedure of Example 1 is followed in preparing each o the compositions.

`:

Z2~3 COMPONENT A
Al Hydrogenated tallow fat~y acids A2 Distllled coconu~ oil fatty acids A3 Distilled tallow fatty acids A4 Cll l3 SYnthetiC fatty acids A5 C22 ~atty aclds A6 Commerclal stearic acids A7 Neat soap ~15:85 A2 soap:A3 soap ~ 33% water) lQ A8 Soap noodles (85/15 tallow coconut ~ 12% wa~er) COMPONENT B
Bl Nonionic reaction product of 1 mole o~ C14 15 primary alkanols with about 11 moles o~ ethylene oxide ~ 11 E.O.) B2 Nonionic C12 15 primary alkanols + 11 E.O.
B3 Nonionlc C12_15 primary alkanols ~ 7 E.O.
B4 Nonionic Cg 11 primary alkanols ~ 5 E.O.
B6 Nonionic C~l 15 secondary alkanol ~ 3 E.O.
B7 Nonionic C16 alkanediol (omega omega) + 5 E.O.
B8 ic sodium C10-l4 ~a~- dodecyl) alkyl benzene sulfona~e B9 Anionic sodium sulfate of lauryl alcohol + 3 E.O.
B10 Anionlc sodium Cl4-17 paraffln sulfonate Bll Anlonic sodium lauryl sulfate B12 Nonionic C8 primary alcohol + 2. E.O.
B13 Nonionlc C12 14 primary alcohol + 2. E.O.
B14 Pluronic L-61 B15 Nonyl phenol ~ 9.5 E.O.
B16 Cl~ 18 ole~in sul~onate B17 Nonlonlc Cll 15 secondary alcohol ~ 5 E.O.
B18 Nonionic Cll_l5 secondary alcohol ~ 7,E.O.
3Q Bl9 Nonionic Cll-15 secondary alcohol ~ 9 E.O.

CO~PONENT C
Cl Ben~yl aIcohol C2 Lauryl alcohol C3 Terpineol C4 D;ethyl phthalate C5 Phenethyl alcohol C6 Propylene glycol C7 Ethylene glycol monoethyl ether C8 Diethylene glycol C9 Triethylene glycol C10 Polye~hylene glycol M.W. 3000 Cll Triethanolamine C12 Glycerine C13 Dipropylene glycol COMPONENT D
:
Dl 35% a~ueous caustic soda solution D2 Deioni~ed water D3 49% aqueous caustic soda solution ~4 50% aqueous caustic potash solution ADDITIVES E
El Optical dye, e.g.
fi2 Dye, e.g. Pigmasol Blue 5G
B3 Perfume .

~ l ~ L, .~fS~

TABLE II - EXAMPLES

.. ..
EXAMPLE COMPONENTS - PARTS BY WEIGHT
. _ A B C DADDITIVES
_._ _._

4 15Al 15Bl 20Cl 5D2 20B17 20C6 4.9D3 lOAl 20Bl 20Cl 5.D2 20B18 20C6 3.3D3 6 8.5Al 26.5BA 23.5C] lOD2 23.5Cl 2.9D3 7 10.6Al 27Bl9 23.5Cl lOD2 23.5Cl 3.2D3 9.4Cl 7A lOAl 20B4 15Cl 1.7D2 20B14 5C6 3.3D3 8 8A6 20Bl 20Cl 2D2 20B18 20C6 2.7D3 9 lOAl 35Bl 25Cl 3D2 .003E2 23C6 3.3D3 lOAl 28B10 28.6Cl 4.4D3 .004E2 28.6C6 11 12.5Al 15Bl 22.5Cl 6D2 .004E2 20B8 22.5C6 4.lD3 12 lOAl 30Bl 56Cl 2D2 4.lD3 13 lOAl 35Bl 20Cl 5D2 lOB6 5C6 3.5D3 lOCll 14 7Al 16Bl 25Cl 5D2 5B15 5Cll llAl 45.2B10 11.4Cl10.5D3 llA2 11.4C6 16 llAl 45.2Bl 11.4Cl 10.5D3 llA2 11.4C6 17 llAl 45.2B8 11.4Cl lO.SD3 llA2 11.4C6 18 llAl 35.2Bl 11.4Cl 10.5D3 llA2 lOB8 11.4C6 19 7A6 18Bl 26.7Cl 2D2 .002E2 16B10 26.7C6 3D3 02F.l ~ ~ _ _ :
_ 29 -- :.- .:' 132~ 3 TABLE II - EXAMPLES (CONT'D).

EXA~PLE COMPONENTS - PARTS BY WEIGHT
._ I
A B C D ADDITIVES
8Al 16B6 19.3Cl 3.6Dl .004E2 13.3B10 19.3C6 2D2 .12El 21 9Al 25B9 27.9Cl 3.2Dl .02El 27.9C6 004E2 22 8A6 35B2 25Cl 2D2 .002E2 25C8 2.8D3 23 3.5Al 33Bl 26Cl 5.lDl 3.5A2 26C6 3.5A3 24 3Al 28Bl 26Cl 1.2Dl 3.5Al 33Bl 20Cl 5Dl 26 8A6 48B2 20Cl 2.8D2 .005El 20C6 2D3 .OOlE2 .3E3 27 8A6 48B2 20Cl 2.8D2 .005El 20C6 2D3 .OOlE2 5C7 lD4 .03E3 28 8A6 20B2 15Cl 4Dl 20B13 lOC6 lD4 lOB10 15C7 29 8A6 20B2 15Cl 4Dl lOB10 lOC6 5D2 20B13 15C7 lD4 7Al 5Bl 37.5Cl 7Dl 7A2 5B8 37.5C6 31 lOAl 14Bl 24.6Cl 4.4Dl .002El 14B10 20.8C6 2.4D2 3E3 32 lOAl 28B2 28.6C2 3.2Dl .OQlEl 28.6C6 .004E2 .3E3 33 lOA8 50B2 20C6 .5bl 34 4A6 50B2 20Cl 2.7Dl :005El SA8 20C6 _ .003E2 .

2~3 TABLE II EXAMpLES (CONT'D~.
~ _ _ ~
EXAMpLE COMPONENTS - PARTS BY WEIGHT
. A B C ¦ D ADDITIVES
10A8 50B2 20Cl .5Dl .005El 81C2C13 .003E2 36 6A6 20B2 28Cl 8Dl .004El 10A4 28C6 .002E2 .35E3 37 6A6 20B2 14Cl 8Dl .004El lOA4 284CC46 . 002E2 38 6A6 20B2 30Cl 3Dl .004El 39 5A5 65Bl 15Cl 1.7Dl lOA5 50Bl 20C5 3.3D4 5Bll 15C6 41 12Al 40B3 22C3 6D2 42 12.5Al 28Bl 20Cl 4Dl 43 3A6 70Bl 20Cl 1.3Dl lA5 6C6 2D2 44 SAl 37.5Bl 15Cl 1.7Dl : 37.5Bl9 SC6 2.5D2 10Al 70B2 15Cl 5.lDl . _ _ _ ~ 31 - : :

.
. , .
:. ' E~MPLE 46 .
Examples 1~ 2 and 3 are repeated with similar re-sults, when the hydrogenated tallow fatty acids in Formula-tion 1 are replaceably.
(A) Distilled coconut oil fatty acids (B) 1:1 mixture of (A) and hydrogenated tallow fatty acids (C) Commercial stearic acid (D) 1:1 mixture of (A) and (C) (~) Pal~itic acid (F) 1:1 mixture of (E~ and hydrogenated tallow fatty acids EXAM
Examples 1-4 are repeated, with similar results, when the ben~yl alcohol is replaced by an equivalent amount of phenethyl alcohol and the propylene glycol by an equiva-lent amount of polyethylene glycol, M.W. 3000.
The products of all the foregoing examples are acceptable with most being excellent if not outstanding.
This invention has been disclosed with respect to preferred embodiments thereof and it will be understood that modifications and variations thereof will become obvious to those skilled in the art and which are to be included within the spirit and purview of this application and the scope of the appended claims.

~ _ ~ _

Claims (22)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A detergent composition comprising

1. a matrix of (A) soap, (B) synthetic detergent, and (C) solvent component; the soap component (A) constituting from 2 to 25%
by weight of the matrix, comprising an alkali metal, alkaline earth metal, ammonium or amine salt of a C6-30 fatty acids said soap component providing in the matrix not more than about 14% of salts fatty acid of more than 18 carbon atoms and not more than 20% of salts of C18 or greater fatty acids and with the further proviso that when potassium soap is present the total soap may be increased to twice the amount of soap used in the potassium salt form and wherein the soap has a weighted average carbon content of at least C14; the synthetic detergent component (B) constituting from 5 to 88%
by weight of the matrix and comprising at least one water soluble number of the group consisting of anionic organic sulfonates, anionic alcohol sulfates, anionic ether sulfates, anionic ether phosphates and nonionic aliphatic detergents but a maximum of about 50% when said synthetic detergent com-ponent (B) consists essentially only of anionic organic sulfon-ates or anionic alcohol sulfates or mixtures thereof, and the solvent component (C) constituting from 10 to 70% by weight of the matrix and comprising a normally liquid, substantially non volatile organic solvent having a boiling point of at least about 100 C, at least 10% thereof being water insoluble and providing at least 10% thereof in solvent compound C, said non-volatile solvent including not more than about 90% thereof of a water soluble solvent including sufficient dihydric alcohol to provide 10% and in the non-volatile com-ponent when water soluble component is present;
II. a water component (D) constituting from 1 to 35 parts per 100 parts of said matrix 1, said matrix and water component being adapted to yield water soluble, soft, spreadable, form stable, solid, shaped detergent articles.

2. A composition as defined in claim 1 wherein the matrix contains about 4 to 15% of component A, about 25 to 76 of component C, said composition containing about l to 15% of water as component D.

3. A composition as defined in claim 1 wherein said fatty acids average at least 12 carbon atoms per molecule.

4. A composition as defined in claim 3 wherein component A comprises the alkali metal salts of mixtures of palmitic and stearic acids.

5. A composition as defined in claim l wherein at least about 40% of component B is an aliphatic non ionic detergent.

6. A composition as defined in claim 5 wherein said aliphatic non ionic detergent is a reaction product of about 2 to 50 moles of ethylene oxide with 1 mole of C8 -20 saturated aliphatic alcohol.

7. A composition as defined in claim 1 wherein at least about 40% of component B is an anionic alkali metal, ammonium or amine salt of an alkylaryl sulfonic acid, an alpha-olefin sulfonic acid, a paraffin sulfonic acid, an alcohol sulfate, or a sulfate ester of the reaction product of about 1 to 20 moles of ethylene oxide with 1 mole of a reactive hydrogen-containing compound of about 8 to 24 carbon atoms.

8. A composition as defined in claim 1 wherein said substantially water insoluble portion of component C comprises benzyl alcohol and said water soluble portion of component C
comprises propylene glycol.

9. A composition as defined in claim 8 containing about equal amounts of said water insoluble and water soluble portions of component C.

10. A composition as defined in claim 9 wherein at least about 40% of component A are the alkali metal salts of hydrogenated tallow fatty acids, and at least about 40% of component B is the non ionic reaction product of about 2 to 50 moles of ethylene oxide with 1 mole of a C8- 20; saturated aliphatic alcohol.

11. A composition as defined in claim 1 wherein said matrix contains about 0.8 to 5.7 parts of component B per part of component A, about 1 to 8.6 parts of component C per part of component A, and about 0.53 to 6.8 parts of component C per part of component B.

12. A composition as defined in claim 1 further con-taining about 0.1 to about 5% by weight of a free alkali metal hydroxide.

13. A method of preparing a composition as defined in claim 1 comprising melting the free fatty acids contained in component A, mixing the molten fatty acids with component C to produce a homogeneous liquid, and admixing therein, at a temperature above the melting point of said free fatty acids and in the presence of component B and D, sufficient alkali metal -, ammonium-, or amine-salt forming bases to neutralize said fatty acids whereby to form their alkali metal, ammonium or amine salts in situ.

14. A method as defined in claim 13 wherein at least about 40% of component B is an aliphatic nonionic detergent and said salt forming base is an alkali metal hydroxide.

15. A method of preparing a composition as defined in claim 1 comprising melting the free fatty acids contained in component A, mixing the molten fatty acids with component C and any non-heat sensitive B components at a temperature above the solidi-fication point of the mixture, admixing herein, at said tempera-ture and in the presence of component D, sufficient alkali metal-, ammonium-, or amine-salt forming base to neutralize said fatty acids whereby to form their alkali metal, ammonium, or amine salts in situ, cooling the resulting liquid to just above the solidification point of said salts, and then admixing therein any heat-sensitive B components.

16. A method as defined in claim 15 wherein said salt-forming base is an alkali metal hydroxide.

17. A water soluble, soft, spreadable detergent stick which comprises a composition as defined in claim 1.

18. A water soluble, soft spreadable stick which comprises a composition as defined in claim 10.

19. A method of cleaning a soiled surface comprising applying thereto a composition as defined in claim 1 and then washing said surface with an aqueous detergent solution.

20. A method of cleaning a soiled surface comprising applying thereto a composition as defined in claim 10 and then washing said surface with an aqueous detergent solution.

21. A method of cleaning a soiled surface comprising contacting said surface with a detergent stick as defined in claim 18 to transfer said composition to said surface, and then washing said surface with an aqueous detergent solution.

22. A method of cleaning a soiled surface comprising contacting said surface with a detergent stick as defined in claim 18 to transfer said composition to said surface, and then washing said surface with an aqueous detergent solution.