IE45191B1 - Detergent compositions - Google Patents

Abstract

A detergent mixture in the form of essentially non-sticking transparent, shaped particles, contains a matrix comprising 15 to 50% by weight of soap components, 10 to 65% by weight of non-soapy surfactant components and 10 to 45% by weight of a solvent component and also a water component in an amount from 1 to 35 parts by weight per 100 parts by weight of the matrix. The soap component must be synthesised from alkali metal, alkaline earth metal, ammonium or amine salts of fatty acids having 6 to 22 C and at most 50% by weight of the fatty acid may be unsaturated. The solvent component must consist of solvents having a boiling point of at least 100 DEG C, of these at least 10% by weight being water-soluble polyhydric alcohols or alkanolamines and at most 90% by weight water-insoluble solvents. The detergent mixture has a high washing power, and in the form of pellets is readily pourable and easily soluble.

Description

This invention relates to detergent compositions, and more particularly to a detergent composition which can be formed into solid, transparent, form-stable, non-sticky, free-flowing substantially non-hygroscopic . pallets, to the .pellets made from such cosiposition, and to methods for making such composition and pellets.

Transparent soaps, and methods for their manufacture, have been well knot® and available for a great . many years. Being costly to manufacture, they have been generally regarded as luxury items, and their transparent properties have been equated with high purity and5neutrality. Such products have been intended almost exclusively for toilet, purposes, e.g. for bathing and for hand and . face washing. In common with opaque soaps, they are not well suited for clothes laundering, their cleansing efficiency being poor cospared with synthetic detergents, particularly in hard water and with respect to some synthetic fibrous materials.

. In U.S. Patent 3, 562,167, there are disclosed transparent detergent compositions, which compositions are said to' be adaptable for forming detergent bars and j calces useful in hard water. Such compositions, bars and - cakes, and the methods disclosed for their preparation, . have been found to be subject to a number of disadvantages.

• More particularly, the products are hygroscopic whereby. the resulting bars and cakes readily absorb moisture from the atmosphere, especially under conditions of high relative humidity, become sticky, and lose their transparency.

. Stickiness is of course particularly objectionable in pallet 2. 45i8i compositions in view of the many points of contact between the pellets. Further, the products are inferior in water-solubility and detergency which are important properties in a detergent composition, . particularly of the pellet type.

According to one aspect of this Invention a detergent composition capable of being formed into solid, transparent, non-tacky, free-flowing pellets comprises: . (i) a matrix of (A) a water-soluble soap component, (B) a water-soluble synthetic detergent component, and (C) a solvent component; the soap component (A) constituting from 15 to 60% of the matrix and comprising an alkali metal, alkaline earth metal (e.g. magnesium), ammonium or amine salt of . Cg_22 fatty acids ox* a mixture of such soaps, the soap component providing in the matrix not more than 30% of salts of fatty acids cf more than 18 carbon atoms, and of the soap present no cc -..’a than 70% is salts of C-jg fatty acid and no more than 50% is salts of unsaturated fatty acids, . no more than 23% of the said salts being potassium salts, and wherein the soap has a weighted average carbon content of at least ¢-54, the carbon content of unsaturated acids being calculated on the basis of actual carbon content mlrius 6; - the synthetic detergent component (B) constituting from 10 to 65% of the matrix and comprising at least one water-soluble member of the group consisting of anionic organic sulphonates and phosphonates, anionic sulphates and phosphates, anionic ether sulphates and phosphates, anionic ^10-20 acy* ssreosinates, isethionates and taurides, and nonionic aliphatic detergents, but a maximum of 35% when 3. 4S191 the synthetic detergent component consists only of anionic organic sulphonates Or anionic alcohol sulphates or mixtures thereof; and the solvent component (C) constituting from 10 to 45% of the matrix and comprising at least one normally liquid, substantially non-volatile organic solvent having a boiling poiht of at least 100¾. at least 10% thereof and at least 10% of component (C·) being a water-soluble dihydric alcohol, and the non-volat'ile solvent including not more than 90« thereof of a water-soluble solvent; and* (II) a water component (D) constituting from 1 to 35 parts of water par 100 total parts of components (Λ), (B) and (C).

All percentages and parts throughout this specification are by weight unless otherwise indicated.

The matrix compositions of this invention are depicted graphically in the accompanying drawing which is a ternary diagram wherein the area bounded by the lines connecting points A, B, C, D, E and ? represent such compositions and the area bounded by the lines connecting points G, H, i, J and K represents preferred matrix compositions.

According to another aspect of the invention a method for preparing the above-defined composition comprises melting free fatty acids for forming soaps for component A, admixing therein components B and C at a temperature above the solidification point of the mixture, and at such temperature and in the presence of component D .admixing therein sufficient alkali metal-, alkaline earth metal-, ammonium- or amine-salt forming bases to saponify or neutralize the fatty acids and form their alkali metal, alkaline earth metal, ammonium or amine salts in situ.

In a modified form of the method just set forth, only non-heat-sensitive B components are admixed with the melted free fatty acids in the first stage, any heatsensitive B components being admixed after the saponification or neutralization step.

. According to a further aspect of the invention a method of preparing pellets from the above-defined composition comprises melting the composition and, while maintaining the temperature of the composition at just above its solidification point in a container provided . at the bottom with means to form drops, such as at least one small aperture, permitting the molten composition to descend from the said means in the form of drops through an atmosphere onto a support, the atmosphere and support being maintained at a temperature sufficiently below the . said solidification point and the support being positioned at a distance sufficiently below the said means to cause at least a substantial proportion of each drop substantially to solidify upon or prior to contacting the support. In this way generally spheroidal or hemi-spheroidal pellets . may be formed.

The detergent composition pellets of this invention can be handled, packaged, stored and employed in much the same manner as the presently available detergent powder, granule and bead compositions, but have the added advantages . of not being subject to dusting, of being less subject to caking, of being more easily handled, particularly by the human hand, and of possessing the highly desirable aesthetic appeal of clear, colourless or coloured.transparency. Their detergency, non-hygroscopic and non-sticky properties represent . further improvements. Although the compositions may contain a significant proportion of water-insoluble solvent in component (C) they are so readily dispersible in an aqueous laundry detergent bath or system that they may be regarded for practical purposes as water-soluble.

The compositions of this invention are especially adaptable to forming into pellets, being formulated to provide optimum fluidity or viscosity properties when melted prior to the pellet-forming step, end to permit the « rapid solidification into pellet shape vzhich seems necessary to achieve the desired transparency and hardness.

Pellets embodying this invention can be made which are transparent, stable, non^tacky and free10. flowing, and which exhibit excellent detergency in clothes.laundering processes, have excellent solubility characteristics particularly in washing machines, and generally have Iqw hygroscopicity so that they are not appreciably physically affected when in a humid environ15. ment (95-100# relative humidity).

The compositions of this invention generally have a soil removal ability comparable to presently used clothes laundering detergent compositions. The detergency is conveniently measured by both the standard Tergotometer . (U.S. Testing Company, Hoboken, New Jersey, U.S.A.) test and with practical machine washes. In the Tergotometer test an aqueous solution of a detergent composition (0.10.550 concentration) is stirred with soiled swatches (and usually with clean swatches as well for redeposition . effectiveness) and the detergency is then determined by before” and after readings on a colour difference meter (e.g. a Gardner. Color Difference Meter). The test may be run at any temperature (generally room temperature to the boil) with stirring at up to 250 r.p.m., for 5 to . 20 minutes (conveniently 10 minutes) at water hardnesses 6. 4S19 1 from 0 to 300 or more ppm (as CaCOj). Prior to the after” readings, the cleansed swatches are rinsed for a few minutes in water of the same hardness as used in the detergency step, dried and then evaluated.

. The dissolution speed of the products of this invention is measured in water at from room temperature to the boil (generally and conveniently at 40°C). The method is generally to add 2 g of product to 500 ml of water at a selected temperature and stir at selected . standardized conditions until all the product is dissolved.

The procedure, specifically, is to use a 600 ml beaker of 12 cm height and 8.5 cm in diameter (very flat bottom) graduated eve”” 50 ml. The 500 ml water is placed in the beaker, the temperature is set, 2g of product is added , and the mixture ia stirred. The stirring is effected by means of a magnetic stirrer which is a cylindrical bar having a 1 nan thick plastics coating. The overall dimensions of the bar are 12 mm diameter and 6,2 mm in length. The speed of x’etation is adjusted to give a vortex with . its apex at the 300 ml graduation of the beaker.

The products of this invention have dissolution speeds when measured as described of from £ to 5 minutes at 40°C.

The penetration hardness of the products of this . invention can be measured by means of the ASTM Method D217-52T (Richardson Method). Values obtained for the products cf this invention vary from about 40 to about 75 (tenths of a millimetre).

The product stickiness (also spreadability and . transferability by rubbing) is determined by rubbing 7. under a 2 kg weight a moulded 1” diameter cylinder of the product on a standard cotton cloth (10 cm long) and measuring the amount of product released hy friction as the cloth is pulled under the weighted cylinder.

- Suitable products have friction values (transferability factors) of from ^50 mg to 200 mg of product per 10 cm atrip of cotton cloth. Preferred products have transferability factors of from <50 rag to about 100 mg.

The.product transparency is conveniently measured . by means ef a lamp photocel/galvanometer system, reading the percentage of transmitted light after a zero adjustment. Spectrooolorimeters can also be used. Substantially total transparency (i.e. ^95%) can be achieved in, products of this invention.

» Other relevant properties 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 compositions, particularly into pellets or other shaped . forms.hereinbefore described. These properties have a direct effect on rate of production, sise and handling of such shaped forms (e.g. pellets) as well as affecting the transparency, stickiness and flowability of the final product. Generally the S.P. of the products of this . invention is in the range from 40°C to 100°G and the viscosity, as measured by a falling ball viscometer, may be in the range from 50 cps to 5000 cps, most suitable values in the range from 1000 to 2000 cps.

Subject to the limitations discussed below, the . fatty acids employed in making the soaps of component A 8. 43191 may contain about 6 to 22 or more, preferably 8 to 18, 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 illustrative of such acids, there may be mentioned caproic, caprylic, capric, lauric, myristic, stearic, oleic, elaidic, isostearic, palmitic, undecylenic, tridooylenic, pentadecylenic, and 2-lower alkyl higher alkanoic (such as 2-methyl tridecanoic, 2-methyl . pentadecanoic or 2-methyl heptadecanoic) acids. Dicarboxylic acids may also be used, such as dimerized linoleic acid. Other high molecular weight acids such as rosin or tall oil acids, e.g. abiotic acid, may be employed.

For the attainment of optimum solubility, hardness, . viscosity, melting and solidifying properties, mixtures or blends oi the above and other types of fatty acids are preferably employed containing no more than 10% of fatty acids containing nore than 18 carbon atoms, and preferably at least 3% but no more than 70% of 18 carbon atom fatty acids. One 9preferred class of fatty acid blends may, for example, contain 0-5% of Cg, 0-10% of C10, 0-30% of C]2, 0-20% of C^, -50% of C^g and 5-70% of C^g saturated fatty acids.

Readily available commercial blends, and mixtures of such blends for obtaining the most suitable distribution of fatty acids, which may be employed include distilled palm and palm kernel oil fatty acids, distilled coconut oil fatty acids, hydrogenated tallow fatty acids and commercial stearic acid. The fatty acid content, in parts by weight, of several such blends, and mixtures thereof, are illustrated in the following Table: TABLE A 8 · C D E F G HC8 - 4.0 * 2.0 - 2.0 1.3 2.7C10 - 3.0 8.5 1.5 - 1.5 1.0 2.0C12 - 45.0 66.2 22.5 - 22.5 5.0 30.1C14 3.0 19.0 25.0 11.0 - 9.5 8.3 13.7C15 30.0 11.0 - 20.5 50+5 30.5 23.7 17.4C18 65.0 4.0 - 34.5 43+4 23.5 44.6 24.3 Max. UnSat. 2.0 12.0 - 7.0 4.0 8.0 5.0 8.7 In the above table, s a 191 A =· commercial hydrogenated tallow fatty acids B = commercial distilled coconut oil fatty acids C = commercial synthetic fatty acids D = 1:1 mixture of A and B (preferred) E = commercial stearic acid F = 1:1 mixture of B and E G = 2:1 .re of A and B H = 1:2 mixture of A and B For the in situ saponification of these fatty acids according to the method of this invention there may be employed any alkali metal-, alkaline earth metal-, ammonium- or amine-salt forming base, for example sodium, potassium, magnesium or ammonium hydroxides, mono-, di- or triethanol-, or -propaneι-amines, or any other such base yielding a water-sc·! Xi salt or soap of the fatty acid being saponified. The base is preferably in the form of a concentrated aqueous solution, for example of 20 to 49% concentration, and at about che temperature cf 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 bats.

The component A soap, apart from its known detergency function, contributes body, hardness and non-sticky properties to the . «19 t pellets. However, the use of more than 50% of component A in preparing the matrix unduly raises the melting or fluidizing temperature (to about 11O°C or more), the viscosity of the hot melt and the rate of solidification . · thereof, thereby preventing proper operation of the pellet-making process, and tends unduly to reduce the transparency and rate of dissolution of the resulting pellets. The use of less than about 15% of component A, on the other hand, may unduly reduce the viscosity %, of the hot melt and the rate of solidification thereof, in addition to yielding pellets v/hich are too soft and sticky at any proportion of components B and C.

In general, it is preferred to employ the fatty lg. acid soap component A in the form of alkali metal salts, such as the potassium and, more preferably, sodium salts, or mixtures thereof. Too high a proportion of potassium soaps has been found to yield products v/hich are unduly opaque and soft, and accordingly no more than 25% of the . component A soaps should be potassium soaps. Preferably at least 50%, up to 100%,of component A should be sodium soaps.

The matrix may contain 15 to 50%, preferably 20 to 45%, and still more preferably 25 to 35% of component A, of which preferably at least 40% is constituted by alkali metal salts of hydrogenated tallow fatty acids and/or at least 35% is constituted by alkali metal salts of distilled coconut oil fatty acids.

As component B there may be employed substantially 12.

S1 91, any water-soluble synthetic organic detergent, or mixtures thereof, of the anionic sulphonate and sulphate and nonionic aliphatic types, ample descriptions of which appear in McCutcheon’s Detergents . and Emulsifiers, 1969 Annual, and in Surface Active Agents by Schwartz, Perry and Berch, Vol. II, 1958 (Interscience Publishers).

Suitable anionic water-soluble detergents include the alkyl aryl sulphonates, especially higher . alkyl (10-20 carbon atom) benzene sulphonates, preferably alkyl benzene sulphonates wherein the alkyl group contains 10 to 16 carbon atoms. The alkyl group is preferably linear and especially preferred are those of average alkyl chain lengths of 11 to 14 carbon atoms, , ' such as linear dodecyl benzene sulphonates.

Preferably also, the alkyl benzene sulphonate has a high content of the meta isomer and a correspondingly low content (welt oelow 50%) of the ortho and para isomers. One suitable type ef such detergent is described in U.S.

. Patent 3,320,174.

Also, typical of the useful anionic detergents are olefin sulphonates. Generally they contain long chain alkenyl suplhonates or long chain hydrcxyalkane sulphonates (with the-OH being on a carbon atom which is not directly · attached to the carbon atom bearing the -SO3 group).

More usually, the olefin sulphonate detergent comprises a mixture of these two types of compounds in varying amounts often together with long chain disulphonates or sulphatesulphonates. Such olefin sulphonates are described in . many patents, such as U.S. patents, such as U.S. patents 13. 4SlSi 2,061,613; 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 hy Baumann et al in Fette-Seifen-Anstrichraittel, Vol. 72, No. 4·, at pages 247-253 (1970). As indicated in those g. patents and the other published literature, the olefin sulphonates may be made from straight chain alpha-olefins, internal olefins, olefins in which the unsaturation is in a vinylidene side chain (e.g. dimers of alpha-olefin), or more usually, mixtures of such compounds, with the . alpha-olefin usually being the major constituent. The sulphonation is usually carried out with sulphur trioxide under low partial pressure^ e.g. sulphur trioxide highly diluted with inert gas such as sir or nitrogen or under vacuum. This reaction generally yields an alkenyl sulphonic . acid, often together with a sultone. The resulting acidic material is generally then made alkaline and treated to open the sultone ring to form the corresponding hydroxyalkane sulphonate and/or alkenyl sulphonate. The number of carbon atoms in the olefin is usually in the range from , 10 to 25, more commonly 12 to 20, e.g. a mixture of principally C12» C14 and Cig having an average of about 14 carbon atoms, or a mixture of principally C14, C16 and Cig having an average of about 16 carbon atoms.

Another class of water-soluble synthetic organic . anionic detergents includes the higher (10 to 20 carbon atoms) paraffin stdphonates. These may be primary paraffin sulphonates made by reacting long chain alphaolefins with bisulphite, e.g. sodium bisulphite, or paraffin sulphonates having the sulphonate groups distributed along the paraffin . chain, such as the products made by reacting a long chain 14. a i g ι paraffin with sulphur dioxide and oxygen under ultraviolet light, followed by neutralization with sodium hydroxide or other suitable base (as in U.S. patents 2,503,280; 2,507,088; 3,260,741; 3,372,188; and German Patent , 735,096). The hydrocarbon substituent of the paraffin sulphonate preferably contains 13 to 17 carbon atoms and the paraffin sulphonate will normally be a monosulphonate but, if desired, may be a di-, tri- or higher sulphonate. Typically, a paraffin disulphonate may be employed in , admixture with the corresponding monosulphonate, for example, as a mixture of mono- and di- sulphonates containing up to 30% of the disulphonate.

The hydrocarbon substituent of the paraffin sulphonate will usually be linear, but branched chain , paraffin sulphonates can fc·. also employed. The paraffin sulphonate used may be terminally sulphonated or the sulphonate substituent may be .joined to the 2-carbon or other carbon atom ·.' the chain, Similarly, any di- or higher sulphonate employed may have the sulphonate groups , distributed over different carbons of the hydrocarbon chain.

Additional water-soluble, anionic detergents Include the higher (e.g. !-;q_2q) acyl sarcosinates, isethionates and taurides such as sodium lauroyl sarcosinate, the oleic acid ester of isethionic aoid, and sodium or potassium · N-methyl-N-lauroyl or -oleyl taurides. Another type of anionic detergent is a higher alkyl phenol mono- and/or di-sulphonate, such as one having an alkyl group of 9 to 25 carbon atoms, preferably a linear alkyl group of 16 to 22 carbon atoms, -which may be made by sulphonating the . corresponding alkyl phenol to a product containing in . - , excess of 1.6, preferably above 1.8, e.g. 1.8 to 1.9 or 1.95 SO^H groups per alkyl phenol molecule.

In these sulphonates, the phenolic hydroxy group may be blocked, as by etherification or esterifica5. tion; thus the H of the phenolic OH may be replaced by an alkyl, e.g., ethyl, or hydroxyalkoxyalkyl, e.g., a “(CH2GHg0)xH group in which x is 1 or more, such as 3, 6 or 10 and the resulting alcoholic OH aay be esterified to form, say, a sulphate, e.g», -OSO^Na.

. Still another type of anionic detergent is a Cg_20 alkanoyl, e.g. coconut oil fatty acid, mono-, di- or tri-glyceride sulphonate.

The above described types of synthetic detergents are representative of the anionic organic . ' sulphonates useful as or in component B.

Other suitable anionic detergents useful as or in component B are anionic organic alcohol sulphates, i.e. sulphate esters of an OH group-containing hydrophobic or oleophilic moiety, such as Cg_20 alkyl sulphates, . e.g. lauryl and tallow alcohol sulphates, alpha- and omega- methoxy octadecyl sulphate, Cg„20 alkanoyl (e.g. coconut oil fatty acid mono- and di-glyceride sulphates, and higher alkyl (¢9.,25} phenol sulphates.

Still other suitable anionic detergents useful . as or in component B are ether sulphates whieh are sulphate esters of nonionic detergents, i.e. the reaction products of from 1 to 20 moles of a C2-4 alkylene oxide, preferably ethylene oxide, with 1 mole of a 0θ_24· reactive hydrogen-containing aliphatic or alicyclic 3®· compound including aliphatic and alicyclic alcohols such 4&1S1 as lauryl, tallow, oxotridecyl, coconut oil, and 1 abietyl alcohols, aliphatic dihydric alcohols such as polyoxypropylenated ethylene and propylene glycols, diamines, and dithiols, aliphatic and alicyclic ear5·. boxylic acids such as stearic acid, erucic acid and abietic acid, aliphatic mercaptans such as dodecyl mercaptan, aliphatic and alicyclic amines such as stearyl amine and rosin amine, and aliphatic amides such as stsaryj aside, or with 1 mole of a . reactive hydrogen-containing aromatic compound including alkyl phenols such as nonyl phenol or dinonyl phenol.

While the aforementioned types of anionic organic sulphates and sulphonates are generally , preferred, it will be understood that the corresponding organic phosphates (see e.g, U.S. Patent 3,595,968) and phosphonates are also useful anionic detergents in component B.

The anionic detergents are preferably salts . of alkali metals, such as potassium and especially sodium, although salts of ammonium cations and substituted ammonium cations derived from lower (2 to 4 carbon atoms) alkanolarnines, e.g triethanolamine, tripropanolamine, diethanol monopropanolamine, and from lower (1 to 4 carbon · atoms) alkylamines, e.g. methylamine, ethylamine, secbutylamine, dimethylamine, tripropylamine and tri-isopropylamine, may also be utilized.

The aliphatic nonionic detergents useful as or in Component B may be reaction products of 2 to 50 moles of . a C2-4 alkylene oxide, preferably ethylene oxide, with 1 17. mole of a Gg_24 reactive hydrogen-containing aliphatic compound, illustrative of which are those reactive hydrogen-containing compounds discussed above ad precursors of sulphate esters of nonionic detergents · which are aliphatic.

Preferred nonionic detergents are those represented by the formulas Η0(σ2Ηώ0)ηΗ wherein R represents the residue of a saturated straight θ· or branched chain aliphatic alcohol, preferably a primary alkanol of 8 to 20, preferably 12 to 18, carbon atoms and n is an integer from 2 to 50, preferably 3 to 20.

Typical commercial nonionic detergents which are suitable include an ethoxylation product, having an · average of 11 ethylene oxide (E.Q.) units, of a 14 to carbon atom chain fatty alcohol; a 12 to 15 carbon atom chain fatty alcohol ethoxylated with an average of 7 E.O. units; a 16 to IS carbon alkanol ethoxylated with an.average of 10 to 11 E.O. units and the reaction θ· products of an average of 11 moles E.O. with 1 mole of a g14-15 primary alkanol, of 5 moles E.O. with 1 mole o£ a Cg„5-s primary alkanol, and of 7 moles E.O. with 1 mole of a C^g-15 primary alkanol; and 3:1 of 1:3 blends of the reaction product of 20 to 50 moles E.O. with * 1 mole of a C^g^8 primary alkanol, and of 3 to 5 moles E.O. with 1 mole of a Cg_-)Q primary alkanol. It will be understood that when a compound is indicated as containing a range of carbon atoms, it is actually one or a mixture of compounds individually having a carbon atom θ' content within such range. Indicated E.O. values are 18, *5191 similarly averages.

Other suitable nonionic aliphatic detergents include liquid and semi solid reaction products of 3 to 20 moles E.O. with 1 mole of secondary · alkanols, the reaction products of 5 to 7 moles E.O. with 1 mole of C^g_jg alkane diols and the Pluronics including the reaction products of 2 to 20 moles E.O. with high molecular weight (e.g, at least 150) polyozvoropylenated ethylene and propylene . glycols, diamines and dithiols (PLURONIC is a trade mark).

As already indicated mixtures of the abovedescribed detergents may be employed as component B.

A preferred form of component E comprises at least 50% . preferably 65%, up to 100%, cf a nonionic aliphatic detergent, especially the nonionic reaction product of 2 to 50, preferably 5 to 15, moles of ethylene oxide with 1 mole v. a saturated aliphatic alcohol, preferably a primary alkanol, of 8 to 20, preferably . 11 to 16, carbon atoms, any balance being an anionic organic sulphonate or sulpnate detergent. Another form of component B contains at least 30, up to 100?,, of an anionic organic ether sulphate detergent. Examples include those wherein component B contains . substantially 100% of the nonionic aliphatic detergent, such as the one described immediately above, or about 70% of such nonionic detergent and about 30% of the anionic detergent such as an alkylaryl sulphonate, especially sodium dodecylbenzene sulphonate, or sub30. stantially 100% of the anionic ether sulphate detergent 19. 43191 . such as sodium lauryl polyethyleneoxy (2-9 E.O.) · . sulphate.

The detergents of component B contribute improved hard water solubility and improved detergency .5. to the compositions and pellets of this invention, particularly in hard water and/or with respect to synthetic fibrous materials such as nylon, polysters such as '’’Dacron and polyacrylonitriles such as Orion and *AcriIan. They also increase the water-solubility , and rates of wetting and dissolution of such compositions and pellets. Generally they should not constitute more than 65%, preferably no more than 55%, of the matrix to avoid the production of increasingly softer, tackier, more hygroscopic and less transparent products. Component . B should contain little or no mineral salts, a fairly common ingredient of commercial detergent formulations, to avoid detrimental effects on the transparency of the products, and may be employed in the matrix in amounts in the range from 10 to 65%, preferably 20 to 55%, and „ still more preferably about 30 to 45%.

A major portion (> 50%), preferably from 75 to 100%, of the solvent component C should be normally liquid, i.e. with a solidification point (S.P.) below 4O°C5 preferably below room temperature, and a boiling . point of at least 100°C, preferably at least 120°C, up to 400°C. It should be substantially non-volatile, with a negligible vapour pressure at room temperature and negligible loss by evaporation on ageing or storage.

, Thus, particularly good non-volatility is indicated by . a loss of weight of 5% or less after 2 hours at 105°C .

*Dacron, -Orion and *Acrilan are trade marks «slsi or after 10 hours at 43°C for a 20 gram sample of solvent in a container with an evaporating surface of about 46.5 cn4 (2.3 sq. inches) placed in an oven provided with a flow of air.

. Of the non-volatile fraction of component C, at least 10% should be a dihydric alcohol to provide 10% thereof in component C and preferably at least 25% up to 100%. One or more substantially waterinsoluble organic solvents, such as benzyl alcohol, , may constitute a part of the non-volatile fraction in an amount not more than 90%, more preferably less than 75%, and still more preferably not above 50« of the non-volatile fraction.

A particularly suitable water-soluble organic , solvent is propylene glycol. Preferably, the ratio of water-insoluble to water-soluble solvents in component C will fall within the range from 1:10 to 10:1, more preferably from ?:'i to 1:10, and most preferably from 1:1 to 1:10. Other suitable ratio ranges are 1:2 to 1:10 . and 1:4 to 1:10.

For the purposes of this invention and solely as a general guide, a solvent may be considered waterinsoluble if its solubility in water at 20°C is less than 10%, preferably less than 5%. Benzyl alcohol which , is one of the preferred water-insoluble solvents has a reported solubility of 4 g per 100 ml of water at 17°C.

As a suitable substantially water-insoluble organic solvent, benzyl alcohol is preferred, or lauryl alcohol or terpineol, but as illustrative of other such . solvents which may be employed in or as component C, 21. 4ΰ191 there may be mentioned, as a rough guide any such liquid more water-insoluble than benzyl alcohol, including generally any substantially water-insoluble aliphatic, alicyclic or aromatic liquid hydrocarbon, halogenated (iodine, bromine or preferably chlorine) hydrocarbon, hydroxylated hydrocarbon, ether or ester having the above-described properties, for example octane, hexadecane, chlorohexane, chlorobenzene and dichlorobenzene, heptyl, oxotridecyl and hexadecy! alcohols, abietyl alcohol, octanediol, phenethyl alcohol, mono- and di-C^_^ alkyl phenols, phenyl ether, benzyl ether, 1,3dibutoxy benzene, 2-benzyloxyethanol, butyl ether, diethyl- and dibutylphthalates, benzyl propionate, and isopropyl myristate, palmitate and stearate.

Again as a rough guide, tha substantially water-soluble solvent in or as component C may be any such solvent which is more watersoluble than benzyl alcok.s, provided that at least 10% of component C is a water-soluble dihyoric alcohol. The balance (if any) of the water-soluble solvent is a liquid and may be of any type chemically, but is generally a monohydric or polyhydric alcohol, ether alcohol, or amine, such as 1,7-heptanediol, the mono- and polyethylene and propylene glycols which are liquids and are of up to 4000 molecular weight, and the mono-C-j^ alky! ethers thereof, glycerol, diglycerol, 2-pentanol, 1-butanol, mono-, di- and tri-ethanolamine and 2-amino-1-butanol, especially the polyhydric alcohols and the alkanolamines.

The solvent component C is essential for the production of pellets which are transparent and further functions as a coupling or mutual solvent for the 431 91 component A soap and its fatty acid precursor, and the component B detergent. It also fluidizes the melt and facilitates the shaping thereof into pellets which solidify rapidly on cooling in the method for . forming the pellets in accordance with the invention.

It further improves the solubility of the pellet products. Substantially water-soluble solvents in component C are good mutual or coupling solvents for components A and B, and good water solubilizers . of the pellet products, but tend to increase the softness, tackiness and hygroscopicity thereof, particularly solvents of the polyhydric alcohol type, in storage and use. Such tendencies can be controlled by limiting the proportions of water-soluble solvents . and employing water-insoluble solvents in component C as described above. T'he water-insoluble solvent, particularly benzyl alcohol, provides body and formstability to the :..redacts. However, a controlled degree of hygroscopicity in the products may be beneficial in . preventing them from drying out, shrinking and cracking in storage and use. Component 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 In the method of manufacture accord25. ing to the invention.

Component C should not constitute more than 45%, still more preferably no more than 35% of the matrix, to avoid unduly reducing the detergency properties of the compositions and pellets because of the resulting lower . proportions of components A and B, and to avoid unduly 23. . 451^1 increasing the sweating (liquids leakage), hygroscopicity, softness and tackiness of the pellets. In general, the matrix may contain 10 to 45%, preferably 10 to 35% and more preferably 20 to 35% of component C.

. Particularly preferred relative proportions are to 2 parts of component A, 1 to 4 parts of component B, and 1 part of component C, apart from the water component B.

The water component D contributes to a lowering . of the viscosity of the composition in the fluid or molten state, and facilitates neutralization of the fatty acid precursors of the component A soaps In the manufacture of the compositions, in addition to assisting in solubilizing components A and P. Some if not all · the water is conveniently introduced in the form of an aqueous solution of the base or alkaline material employed in the in situ neutralization or saponification of the fatty acid precursors of the component A soap.

Water also increases the water-solubility and transparency . of the pellets and, due to Its partial loss from the pellets by evaporation during ageing and storage, particularly from the outer layers of the pellets, reduces the surface stickiness and increases the hardness thereof. Too low a. proportion of water detrimentally affects the . workability of the compositions and the transparency of the resulting pellets. Too high a proportion unduly reduces the rate of solidification of these compositions into pellets, and unduly Increases the stickiness and softness thereof.

In general the compositions and pellets of this 24. 5191 invention should contain 1 to 35 parts, preferably 5 to 25 parts, and more preferably 10 to 15 parts of water component D, per hundred total parts of ' (A), (B), and (C), and in general no more than 15% . by weight of component D.

According to the method 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, nixing in components . B and C, and gently stirring the mixture at a temperature above, but preferably no more than 50° above, the melting point of the fatty acids until a homogeneous liquid is obtained. A solution of the selected salt-forming base in the water component D, preferably . at the temperature of the homogeneous melt, is then mixed therein, preferably gradually and/or in small Increments to avoid lumps and overheating, until the in situ neutralisation and/or saponification of the fatty acids ir. che melt is complete. Desirably, an . approximately stoichiometric amount of the base is employed to avoid excess base or fatty acids in the product. Neutrality in the product can be ascertained, for example-, by periodic testing with phenolphthalein Indicator, If desired the 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, and introducing the B and C components, in the form of the resulting hot clear solution, into the . molten fatty acids. . aSi01 After all the base has been added and the resulting hot liquid product mixed sufficiently until.it is determined that the fatty acids are neutralized, any desired minor amounts of known . additives for detergent formulations may be mixed in, together with any desired additional amounts of water component D. Alternatively, some of the water component D may be added together with the detergent component 3 and/or the solvent component . C.

In some instances, it may be desirable to replace up to 75% or even more of the initially melted free fatty acids by their corresponding soaps or salts, e.g. neat or kettle soap, with a · ' corresponding reduction in the proportion of soapor salt-forming base subsequently mixed with the hot melt to neutralize or saponify the free fatty acids thei’ein.

In a modified form of the method, when a . product is being prepared containing a heat-sensitive anionic sulphonate or sulphate detergent as or in component B, such detergent is preferably not mixed with the molten fatty acids prior to the exothermic neutralization reaction thereof with the base, but is . instead subsequently mixed into or with the previously neutralized and cooled liquid (cooled to just above the solidification point of the liquid containing the soap or fatty acid salt component A, the solvent component C, and any nonionic aliphatic detergent portion of . component B). 26.

The hot liquid composition produced as described above may if desired be cooled and solidified in bulk or any other desired form.

The cooled and solidified composition may be . reraelted, or more preferably the hot liquid composition may be employed without such intermediate cooling, solidification, and remelting steps and/or evaporation, and used in the method for preparing transparent., watvr-soluhle, non-sticky, substant10. ially non-hygroscopic detergent pellets.

Suitable pellet-preparing methods may include the use of equipment (e.g. pipes, hoppers, containers, nozzles nnd valves) provided with suitable heating means effective for maintaining the temperature of 13. the hot or molten liquid composition at just above its solidification pcinu (i.e, about 2°C up to 50°C, preferably up to 20°C, above the S.P.) until commencement of the formation ... drops falling from a suitable aperture or apertures. Suer. S.P.s may range from as low as 40°C . up to 110°C. If the temperature were permitted to drop to or below such S.P., premature solidification would be initiated prior to the desired drop and pellet formation. The flow of hot liquid composition to and through the aperture would be thereby reduced, impeded or halted . completely. If the temperature is too high, loss of some portions of the components, with consequent changes in the desired optimum proportions or ratios thereof, may occur by decomposition and/or evaporation or the like, and possible concomittant detrimental effects on com30. position and pellet properties such as pelletability 27. '5.

. . . . «Gl®1 (rate of solidification, etc.), viscosity, transparency, hardness, solubility, detergency and hygroscopicity.

Undue loss of volatile components at such high temperatures may further result in premature solidification of soap component A and/or detergent component B in the equipment prior to drop and pellet formation. Still further, if the temperature of the liquid composition in the drops being formed at the aperture is too high, solidification into pellet formation cn the support below the apertures will be prevented, and the still completely liquid drops will strike the support and spatter or form a flat, continuous film thereon.

The viscosity of the hot liquid detergent composition is likewise an important factor, particularly in determining the output rate (rate of drop formation) and the size of the drops. Such viscosities, measured by falling ball viscometer, may range from 50 to 3000 ops, preferably 1000 tc< 2000 ops.

Accordingly, the size of the apertures, the temperature, viscosity arid rate of solidification of the composition in the drops, the vertical distance between the apertures and the support, and the temperatures of the support and the atmosphere between the apertures and the support are interdependent variables to be controlled for achieving the desired formation of pellets vzhich may range in sise (maximum dimension) from about 2 to about 9 w, preferably about 3 to about 5 mm, and may have the shape of a disc, sphere, bean or lentil, tear drop or truncated version thereof.

Generally, there should preferably be a plurality 28. 5191 of apertures, up to 500 or even more, which mayrange from about 0.5 to about 4 mm ln diameter, in the bottom of the container holding the hot liquid composition. The container is preferably . provided with stirring means. The height between the apertures and the support may range from about 0.5 to about 5. preferably 1 to 2 cm. The apertures and/or the container may be provided with vibrating means, preferably vibrating in a vertical direction, . for the purpose of facilitating separation of the drops therefrom and preventing formation of stalactites thereon. Such vibrating means may, for example, vibrate at a frequency of about 0.2 to about 5 cycles per seccnd, and desirably with such amplitude . as to cause contact between the support and the drop as it is forming.

It may bo convenient to provide the support with vibrating means w-’-sreby it may serve an additional function of preventing sticking of the pellets to, and . facilitating removal of the pellets from, the support.

The suppox-t, preferably moving, is cf heat conducive material, preferably metal, such as a rotating cylinder, or still more preferably in the form of an endless moving metal belt provided v/ith means for continuously removing · the pellets, such as angled knife scrapex's, and also optionally provided with additional vertically or horizontally biased vibrating means to prevent sticking of the pellets to the support and facilitate their removal. Such support may service a series of containers continuously . depositing pellet-forming drops thereon. The temperature 29. of the support and the atmosphere through which the drops descend should be well below the S.P. of the hot liquid detergent composition so that, with any particular composition, temperature thereof, size . of drops, height between aperture and support, at least a substantial proportion of each drop is substantially solidified upon or prior to contacting the support. The underside of the support may for example be cooled by air blower or cooling liquid . spray.

The resulting pellets should preferably be aged in warm, dry, air prior to packaging, to promote hardness and non-stickness.

Transparent detergent pellets may also be made 15· from the compositions by methods other than as described above, and may be of any other shape or configuration such as cylinders, cubes, pyramids or cones.

The following Examples illustrate the invention.

Example 1, and the remaining Examples in Table II, 20. in conjunction v/ith Table I, list and describe component ingredients and ths amounts thereof employed in making compositions and pellets exemplary of the invention. In making such compositions, the fatty acids of component A are melted in a heated vessel, the solvent component C . poured in, the detergent component B mixed ih, and the mass heated with gentle stirring at a temperature not more than 50°C, generally not more than 20°C, and usually 2 to 10°C, above the melting point of the fatty acids until a homogeneous liquid is obtained. Such temperatures . may be in the range from 60 to 110°C, generally 70 to 100°C, . ΚΙ 9 I and usually 80 to 90°C. The water component D, with an approximately stoichiometric amount of caustic soda dissolved therein, and at about the temperature of the hot homogeneous liquid, is then gradually admixed therein . to avoid lumps and overheating until the neutralization and/or saponification of the fatty acids is completed. Completion can be ascertained by periodic testing with phenolphthalein indicator, or by adding a few drops of such indicates to the hot homogeneous liquid and . watching for development of a pink shade. In making compositions employing heat-sensitive anionic sulphonated and/or sulphate detergents in component B, such detergents may instead be added to the heated vessel only after neutralization with the caustic soda and the cooling . of the neutralized liquid to from 1 to 5°C above its S.P., to minimize thermal decomposition of the heat-sensitive anionic detergent.

If the hee-'Od vessel in which the mixing and neutralization is conducted is not provided with pellet20. making apertures as described below, the resulting hot liquid compositions are then transferred, while maintaining their temperatures above their S.P.s, to a heated container in the bottom of which are a plurality of apertures of nozzles v/ith adjustable openings ranging · from 0.5 to 2 mm, usually about 1 mm, in diameter. The hot liquid drops forming at the exits of the nozzles descend through an atmosphere at a temperature below the S.?, of the composition for a distance of from about 1 to about 2 cm, onto an endless moving metal belt provided . with vertical vibrating means and cooled to well below 31. -30°C below) the S.P.s. Solidification of the drops commences as they separate from the nozzles and is st least partially completed upon or prior to contacting the belt so that pellets with a maximum « dimension averaging from 2 to 9 mm, usually 3 to 5 mm, are formed. At a suitable distance from the nozzles, an angled knife scraper removes the completely solidified pellets from the belt into a container or conveyer for ageing and packaging, . All the compositions and pellets of the Examples in Table II have acceptable, good or excellent properties with respect to hot melt viscosity, pelletabillty, transparency, hardness, dissolution speed (rate of water solubility), hygroscopicity and detergency.

TABLE i- INGREDIENTS COMPONENT A Al Hydrogenated tallow fatty acids A2 Distilled coconut oil fatty acids A3 Distilled tallow fatty acids A4 ^11-13 synthetic Tatty acids A5 Cgg Fatty acids A5 Commercial stearic acids A7 Neat soap (15:85 A2 soap:A3 soap + 33% water) COMPONENT B Bl Nonionic reaction product of 1 mole of C^_^g primary alkanol with about 11 moles of ethylene oxide (+ 11 £.0.) B2 Nonionic C|2-15 ΡΪ’ΠΒ1·Υ alkanols + 11 E.O. B3 Nonionic €12-15 primary alkanols >- 7 E.O. 84 Nonionic Cg_^ primary a :;:anols + 5 E.O. Be Nonionic C15 seconaary alkanol + 3 E.O. 87 Nonionic alkanediol (omega omega) + 5 E.O. 33 Anionic sodium £,.,.,.,/ (av. dodecyl) alkyl benzene sulphonate. B9 Anionic sodium sulphate of lauryl alcolol + 3 E.O. BIO Anionic sodz'ir. paraffin sulphonate Ell Anionic sodium lauryl sulphate Cl COMPONENT C Benzyl alcohol C2 Lauryl alcohol C3 Terpineol C4 Diethyl phthalate C5 Phenethyl alcohol C6 Propylene glycol C7 Moncethylene glycol C8 Diethylene glycol C9 Triethylene glycol CIO Polyethylene glycol E200 Cll Triethanolamine «,Βΐ®1 TABLE I - INGREDIENTS (Continued) COMPONENT D Dl 35% aqueous caustic soda solution D2 Deionized water 5 D3 49% aqueous caustic soda solution D4 50% aqueous caustic potash solution ADDITIVES E El Optical ctye E2 Dye, e.g. Pigraosol Slue 5G (PIGMOSOL is a trade mark) 10 E3 Perfume TABLE II - EXAMPLES COMPONENTS - PARTS BV HEIGHT Example A 0 C 0 Additives 1 n.oAi 11.0 A2 45.2 81 11.4 Cl 11.4 C6 10.5 Dl 7.0 02 2 14.0 Al 8.0 A2 42.0 BI 12.0 C1 12.0 CS 10.2 01 5.0 02 0.1 El 0.004 E2 3 11.0 Al 11.0 A2 35.2 BI 10.0 58 11.4 Cl 11.4 CS 10.5 01 7.5 02 4 n.o ai 11.0 A2 45.2 B9 15.0 Cl 11.4 C6 10,0 01 5 n.o ai 40.0 BI 12.5 Cl 10.0 DT 0.25 El n.O A2 5.0 34 12.5 C6 4.15 02 0.003 E2 0.30 E3 6 15.0 Al 20.0 A2 10.0 BI 20.0 Cl 20.0 Cl 17.1 Dl 10.0 D2 0.005 E2 7 n.o Al 11.0 A2 45.Z.B2 11.4 Cl 11.4 C6 10.5 Dl 6.0 D2 8 14.0 Al 14.0 A2 25.0 BI 17.5 Cl 17.5 C6 13.4 01 8.0 D2 0.25 El 0.004 E2 0.30 E3 9 14.0 Al 14.0 A2 40.0 BI 5.0 Cl 6.0 C2 6.0 06 6.0 C8 13.4 01 8.0 02 0.25 El 0.003 E2 0.30 E3 TABLE 11 - EXAMPLES (Contd.) COMPONENTS A B C D Additives 14.0 Al 14.0 A2 40.0 B2 6.0 Cl 6.0 C4 6.0 C6 5.0 CIO 13.4 Dl 8.0 D2 0.25 El 0.004 E2 0.35 E3 14.0 Al 40.2 B2 6.0 Cl 13.4 Dl 0.25 El 14.0 A2 6.0 C2 8.0 D2 0.004 E2 4.0 C7 0.30 E3 4.0 C8 4.0 C9 14.0 '! 40.0 BI 6.0 C2 13.4 Dl 0.25 El 14.0 A2 6.0 C3 8.0 D2 0.004 E2 12.0 C6 0.30 E3 15.0 Al 40.0 82 12.0 Cl 12.0 Dl 7.0 A4 12.0 C8 7.0 D2 14.0 Al 25.0 B9 17.5 Cl 34.4 Dl 14.0 A2 17.5 C6 8.0 D2 7.0 A! 22.5 82 15.3 Cl 7.0 Dl 7.0 A2 15.a SiO 15.3 C6 2.0 D2 7.0 Λ3 7.0 Al 22.5 B2 14.3 Cl 7.0 Dl 7.0 A2 15.3 BIO 14.3 C6 2.0 D2 7.0 A3 2.0 Cll 8.0 AT 13.5 B9 18.4 Cl* 8.1 Dl 8.0 I 13.5 BIO 18.4 C6 8.0 73 10.0 Al 7.0 81 15.0 Cl 11.3 D3 20.0 A6 7.0 B6 24.0 C6 5.0 D2 3G*U Al 15.0 BI 10.0 Cl 8.3 D3 25.0 C6 8.3 D2 25.4 Al 21.1 BI 16.9 Cl 7.0 D3 21.1 C6 8.5 D2 30.0 A6 15.0 BI 20.0 Cl 5.0 D2 20.0 C6 10.0 D3 13.0 A! 40.0 BI 12.5 Cl 4.3 Dl 17.0 Λ7 12.5 C6 11.0 A2 35.2 BI 11.4 Cl 10.5 Dl Π.ϋ A2 10.0 Bll 11.4 C6 7.5 D2 Similar good results when 2,5 parts of each of Cl and C6 in Example 17 replaced by cocodiethanol amide. &S19 1 The compositions of this invention, in addition to the aforedescribed characteristics, generally also are. of the low - or lower - foaming type, particularly where the detergent B is nonionic. The combination of . nonionic detergents and nonionic - containing detergent mixtures (with, for example, alkylbenzene sulphonates, olefin sulphonates, paraffin sulphonates and mixtures thereof) with the higher fatty acid soaps is known to give a lov/ - foaming or, indeed, in many cases, a . synergistically low - or lower - foaming product which is especially useful in high temperature (e.g. 60°C to the boil) machine laundering processes. Nonionics of optimum detergency characteristics and in amounts to give acceptable and more than acceptable performance . ore difficult to produce in the form of conventional spray dried products and the present invention, inter alia, makes available outstanding low-foaming compositions, particularly with high nonionic content which affords an effective solution to the problem. . «ΰίθι COMPARATIVE EXAMPLES 24. When 50 parts of 08 are mixed with 50 parts of C6 at about 100°C, the resulting soapless mixture does not solidify on cooling to room temperature.

. Similar results are obtained when Example 24 is repeated substituting Cl for C6. 26. Similar results are obtained when Example 24 is repeated substituting half of the 06 by Cl. 27. Similar results are obtained when Example 26 is repeated substituting Bl for 88. 28. When tne procedure of Example 1 is followed mixing parts of hot Dl into a het molten liquid at about 70°C. containing lu parts of A1. 95 parts of Bl and 95 parts of B6, the resulting hot liquid, containing no solvent component C and too little soap e xponent A, is too viscous when hot, and very soft and opaque when cooled to room temperature. 29. When tne procedure of Example 1 is followed mixing a stoichiometric amount of hot Dl into a hot molten liquid at about 80°C containing 70 parts of Al, parts of Bl and 65 parts of B6, the resulting hot molten liquid containing no solvent component C, is very viscous and aerated, and is hard but opaque and sticky when cooled to room temperature.

The compositions set forth in the foregoing Table II illustrate embodiments of transparent compositions of this invention. While such compositions as hereinbefore described are outstandingly . functional and uncommonly aesthetic, particularly when in pigmented or dyed form, they may also form the basis for detergents of generally similar physical characteristics as to form-stability, size, shape, free-flowsbility, lack cf tackiness or stickiness, . water-solubility, hardness, but of greatly varying properties as to soil removal and foam properties, by the incorporation into such compositions of any of the conventional detergent adjuvants as well as other components as hereinafter described. Among . ' such materials mention aay be made of fillers (e.g, silica, bentonite, insoluble silicates and molecular sieves); inorganic builders (e.g. bicarbonates, borates, carbonates, phosphates and soluble silicates); oxidizing agents (e.g. perborates, percarbonates and persulphates); . organic builders (e.g. aminopoly - carboxylates, such as nitrilotriacetic acid trisodium salt, sodium ethylene diamine tetra-acetate, disodium hydroximinodiacetate and 1, 2 diamino oylclohexane diacetic acid); polyelectrolytes; phosphonates; citrates; gluconates; . brighteners; u-v absorbers; foam regulating agents (e.g. high molecular weight soaps, polysiloxanes and fatty amines); foam boosters (e.g. amine oxides and fatty acids alkanolamides); other surfactants (e.g. cationics, amphoterics and ampholytics); germicides; perservatives.

. Additives of the aforementioned type may be 38. employed in any desired quantitites to effect the desired functional characteristics, thus such components as preservatives, germicides, dyes, pigments and u-v absorbers are generally used in minor amounts, , e.g. 001% up to 10%. Other additives can be used at any level, e.g. fillers (1 to 75%); builders (1 to 85%); foam boosters (1 to 75%); defoamers and foam control agents (0.1 to 20%); sequestrants (0.1 to 20%); oxidizing agents M to 50%).

. Of particular value is the incorporation of builders and additives v/hich may have thermal or other environmental instability. In this regard of particular note is the use of u-v absorbers, brighteners and foam control agents, especially of the polysiloxane type.

. Of the inorganic builders, those which are preferably used are alkali .natal salts, e.g. alkali metal tripolyphosnhetea, pyrophosphates and hexametaphosphates, and from these sodium tripolypheannate (anhydrous, hydrated, hexahydrate) is usually the builder of choice . with tetra potassium pyrophosphate somewhat less preferable due primarily to cost.

The compositions of this invention which include the aforedescribed adjuvents may be similar in appearance (e.g. transparency) to the matrix base itself or . may be more or less transparent, ranging from highly transparent through translucent to opaque. In any event the translucent and opaque products are also of particularly pleasing appearance.

The following Examples illustrate compositions . containing such adjuvants: 39. ΐθ* EXAMPLE 30 parts of the composition of Example 1 (before pelletizing) and while in the fluid state (70°) are thoroughly mixed with 35 parts of anhydrous sodium tripolyphosphate, and thereafter the composition is pelletized as in Example 1. The resulting pellets are free-flowing, non-tacky, readily water-soluble and have excellent laundry performance characteristics. The pellets are a dense, opaque white and have a polished white marble appearance.

EXAMPLE 31 Example 1 is repeated with the addition of 0.2 parts of brightened (*Optiblanc LSM ) added to the composition. The brightener is first dissolved in the solvent and then the procedure followed is similar to Example 1. Excellent transparent pellets are produced.

EXAMPLE. 32 Example 1 is repeated except that the solvent mixture used is 20 parts propylene glycol and 2.8 parts benzyl alcohol.

EXAMPLE 33 Example 1 is repeated except that the solvent is all 20 parts propylene glycol.

EXAMPLE 34 Example 1 is repeated using as the nonionie detergent a ^13-15 ethoxylate containing 11 moles of condensed ethylene oxide per mole of alcohol. *0ptiblanc is a trade mark d S1 9 1 EXAMPLE 35 Example 1 is repeated replacing half the nonionic detergent with component B-3.

EXAMPLE 36 Example 30 is repeated except that in place of the 35 parts of tri polyphosphate there are used 35 parts of a molecular sieve zeolite type A as described in German Offenlegenschriften 2412836 and 2412837. Specifically, the zeolite is type A100 sodium aluminium silicate containing 20% HgO, mean particle diameter 5.9 - 5.4 microns, pore size about 4 Angstroms.

EXAMPLE 37 Example 30 is repeated using 35 parts *Linde Type 4A molecular sieve (Union Carbide Corn.) having an average pore size of 8 Angstroms and an s/erage particle size of 8.3 microns, in place cf the tripolyphospncte.

EXAMPLE 38 Example 30 is repeated replacing half of the tripolyphosphate with an equal weight of the zeolite of Example 36.

EXAMPLE 39 Example 30 is repeated replacing the 35 parts of tripolyphosphate with an equal weight of polyhydroxy acrylic acid lactone.

Claims (24)

1. A detergent composition capable of being formed into solid, transparent, non-tacky, free-flowing pellets and comprising: (I) a matrix of (A) a water-soluble component, (B) a water-soluble synthetic detergent component, and (C) a solvent component: the soap component (A; constituting from 15 to 50% of the matrix and comprising an alkali metal, alkaline earth metal (e.g. magnesium), ammonium or amine salt of a Cg^ fatty acid or a mixture of such soaps, the soap component providing in tha matrix not more than 30% of salts of fatty acid of more than IS carbon atoms, and of the soap present no more than 70% is salts cf C.θ fatty acid and no more than 50% is salts of unsaturated fatty acid, no snore than 25% of the said salts being potassium salts, and wherein the soap has a weighted average carbon content (as hereinbefore defined) cf at least C^; the synthetic detergent component (B) constituting from 10 to 65% of the matrix and comprising at least one water-soluble member of the group consisting of anionic organic sulphonates and phosphonates, anionic alcohol sulphates and phosphates, anionic ether sulphates and phosphates, anionic acyl sarcosinates, isethionates and tauridas and nonionic aliphatic detergents, but a maximum of 35% when the synthetic detergent component consists only of anionic organic sulphonates or anionic alcohol sulphates of mixtures thereof; and the solvent component (Cj constituting from 10 to 45% of the matrix and comprising at least one normally liquid, substantially non-volatile organic 4 S ι g 2 solvent having a boiling point of at least 100°C, at least 10% thereof and at least ^055 of component (C) being a water-soluble dihydric alcohol, and the non-volatile 'Solvent including not more than 90% thereof of a water-insoluble solvent; and II. a water component (D)· constituting from 1 to 35 parts per 100 total parts of components (A), (B) and (C).

2. A composition as claimed in Claim 1 containing from 20 to 45% of component A, from 20 to 55% of component B, from 10 to 35% of component C, and from 5 to 25 parts of water per 100 parts cf matrix,

3. A composition as claimed in Claim 1 containing from 25 to 35% of component A, from 30 to 45% of component 5, from 20 to 35% of component C, and from 10 to 15 parts of water per 100 parts of matrix.

4. A composition as claimed in any of preceding Claims wherein at least 40% of component A is constituted by alkali metal salts of hydrogenated tallow fatty acids.

5. A composition as claimed in any of the preceding Claims wherein at least 35% of component A Is constituted by alkali metal salts of distilled coconut oil fatty acids. 43. -^l 9i

6. A composition as claimed in any of the preceding Claims wherein at least 50% of component B is a nonionic aliphatic detergent.

7. A composition as claimed in Claim 6 wherein the nonionic aliphatic detergent is a reaction product of from 2 to 50 moles of ethylene oxide with 1 mole of a saturated aliphatic aloohol of 8 to 20 carbon atoms.

8. A composition as claimed in any of the preceding Claims wherein at least 30% cf component B Is sn anionic organic ether sulphate.

9. A composition as claimed in Claim 8 wherein the anionic ether sulphate is an alkali metal, ammonium or amine salt of a sulphate ester of the reaction products of from 1 to 20 moles of ethylene oxide with 1 mole of a reactive hydrogen-containing compound of 8 to 24 carbon atoms. ·.

10. A composition as claimed in any of the preceding Claims wherein more than 50% of component C is constituted by water-soluble solvent(s).

11. A composition as claimed in any of Claims 1 to 9 wherein from 10 to 90% of component C is constituted by a water-insoluble component which is ben2yl alcohol, lauryl alcohol, terpineol or a mixture thereof, and from 90 to 10% Is constituted by a water-soluble component which is a water-soluble polyhydric alcohol or an alkanolamine or a mixture thereof. 44. 4 319 3

12. A composition as claimed in Claim 11 wherein from 10 to 50% of component C is constituted hy the said water-insoluble component and 90 to 50% of component C is constituted by the said watersoluble component.

13. A composition as claimed in any of the preceding Claims wherein at least 4G% of component A is constituted by alkali metal salts of hydrogenated tallow fatty acids and at least 35% is constituted by the alkali metal salts of distilled coconut oil fatty acids, at least 50% of component B is constituted by the aonionic reaction product of from 2 to 50 moles of ethylene oxide with 1 mole of a saturated aliphatic alcohol of 8 to 20 carbon atoms, and component D consists of from 5 to 25 parts of water per 100 parts of matrix.

14. Compovi-cions as claimed in Claim 1, substantially as described with reference to Examples 1 to 23 and 30 to 39.

15. · A method of preparing a composition as claimed in any of the preceding Claims comprising melting free fatty acids for forming soaps for component A, admixing therein components B and C at a temperature above the solidification point of the mixture, and at such temperature and in the presence of component D admixing therein sufficient alkali metal-, alkaline earth metal-, ammoniumor amine-salt forming base to saponify or neutralize the fatty acids and form their alkali metal, alkaline earth metal, ammonium or amine salts in situ. 45. ©St 9i

16. A method of preparing a composition as claimed in any of Claims 1 to 14 comprising . melting free fatty acids contained in component A, admixing therein, at a temperature above the solidification point of the mixture, component C and non-heat-sensitive B components, then admixing therein at such temperature and in the presence of component D sufficient alkali metal-, alkaline earth metal-, ammonium- or amine-salt forming base to saponify or neutralize the fatty acids and form their alkali metal, alkaline earth metal, ammonium or amine salts in situ, and then admixing therein at such temperature any heat-sensitive B components.

17. A method as claimed in Claim 15 or Claim 16'wherein at least about 50% of component B is a nonionic aliphatic detergent.

18. A method as claimed in any of Claims 15 to 17 wherein the salt-forming base is an alkali metal hydroxide.

19. Compositions as claimed in any of Claims 1 to 14 which have been made by methods as claimed in any of Claims 15 to 18.

20. Transparent, non-sticky, substantially non-hygroscopic detergent pellets formed of a composition as claimed in any of Claims 1 to 14 or 19. 46. 4 S1 ί) 1

21. Pellets as claimed in Claim 20 having an average maximum dimension in the range from 2 to 9 mm.

22. A method of preparing pellets as claimed 5 in Claim 20 or Claim 21, comprising melting the composition and, while maintaining the temperature of the composition at just above Its solidification point in a container provided at the bottom with means to form drops, permitting the molten composi10 tion to descend from the said means in the form of drops through an atmosphere onto a support, the atmosphere and support being maintained at a temperature sufficiently below the said solidification point and the support being positioned at a distance 15 sufficiently below the said means to cause at least a substantial proportion of each drop substantially to solidify upon prior to contacting the support.

23. A method as claimed in Claim 22 wherein the means to form drops is vibrated in a vertical 20 direction.

24. Pellets as claimed in Claim 20 or Claim 21 which have been prepared by a method as claimed in Claim 22 or Claim 23.