DK155749B - TRANSPARENT, WATER SOLUBLE, NON-COMPLIANT AND IN ESSENTIAL NON-HYGROSCOPIC DETERGENT BOWLS - Google Patents

Description

DK 155749 B

The invention relates to transparent, water-soluble, non-sticky and substantially non-hygroscopic detergent target balls.

Transparent soaps and their processes have been well known and available for a large number of years. Since they are expensive to manufacture, they have generally been regarded as luxury items and their transparent properties have been considered to mean high purity and neutrality. Such products have almost exclusively excluded those used in the toilet articles area, i.e. for use in badni 10 hand and face wash, etc. However, with opaque soaps, they are not acceptable for washing clothes as their cleaning efficiency is deficient, especially in hard water and with respect to some of the synthetic fiber materials.

U.S. Patent No. 3,562,167 discloses transparent detergents which are said to be suitable for forming detergent rods and pieces useful in hard water. Such means, rods and pieces as well as the methods described for their manufacture have been found to suffer from a number of disadvantages. More specifically, the products are hygroscopic, whereby the resulting rods and pieces readily absorb moisture from the atmosphere, especially under conditions of high relative humidity, become sticky and lose their transparency. Obviously, tackiness is particularly inconvenient in pellets in accordance with the present invention in view of the many points of contact that exist between the pellets. Furthermore, the products are inferior in terms of water solubility and washing or cleaning ability, which are of course important properties of a detergent, especially of the small-ball type.

Said United States patent does not disclose free-flowing agents in the form of small balls, i.e. in pellettised form and the agents disclosed in the patent contain saturated fatty acid sodium soaps of at least 18. carbon atoms, especially stearate, while the detergent pellets of the present invention contain a maximum of 70% C18 fatty acid soap and at most 30% soaps with more than 18 carbon atoms. .

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Still, the said US patent does not prescribe a content of 1-35 parts water per 100 parts of matrix, use of non-ionic aliphatic detergents, as is the case according to embodiments of the present invention set forth in claims 6, 7 and 13, or that at least 10% of the solvent component is water insoluble, as is the case in the present invention. Embodiments of the present invention set forth in claims 11 and 12. Finally, the quantity indications prescribed according to embodiments of the present invention set forth in claims 2-6 and 1 13 are also not known from United States Patent No. 3,562,167.

SUMMARY OF THE INVENTION The present invention aims to provide detergent goblets which do not suffer from one or more of the above disadvantages.

15

This is achieved by means of the detergent gob balls according to the invention, which are characterized by the characterizing part of claim 1.

20

Compositions of the matrix component of the detergent goblets according to the invention are set forth in FIG. 1, wherein the area bounded by the lines connecting points A, B, C, D, E and F represents such compositions and the area bounded by the lines connecting points G, Η, I, J and K represents preferred 25 grunts. -dmass composition in nger.

The composition of the detergent beads is obtained by melting free fatty acids contained in component A, admixture therein of components B and C at a temperature above the setting point of the mixture, and, at such a temperature and in the presence of component 0, admixture therein of sufficient amounts of alkali metal, alkaline earth number, ammonium or amine salt forming bases for saponifying or neutralizing said fatty acids, thereby forming their alkali metal, alkaline earth metal, ammonium or amine salts in situ.

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3

The detergent spheres are made from the material of the composition obtained by melting the material and while maintaining its temperature just above its solidification point in a container formed at the bottom with at least one small aperture by moving the molten material downwardly from said aperture. form 5 of droplets through an atmosphere to a temperature sufficiently far below said solidification point, and the support being spaced sufficiently below said opening to cause at least a substantial portion of each droplet to substantially solidify at that or before it comes into contact with the support, thereby forming generally spherical or hemispherical hail or grain.

The detergent spheres of the invention can be handled, packaged, stored and used in much the same way as the detergents available in the form of powders, granules and grains, but they have the additional advantage of not being dusty. less likely to bake together, can be handled more easily, especially manually, as well as possessing the highly desirable aesthetic ten! drawing which results in clear, colorless or color transparency. Their 20 greater water solubility, cleansing, non-hygroscopic and non-adhesive properties further represent improvements and advantages. Furthermore, the compositions of the invention are particularly suitable for molding to the desired beads, being composed to obtain optimum fluidity or viscosity properties when melted prior to the bead forming step, and to achieve the rapid solidification to the bead shape considered necessary. to achieve the desired transparency and hardness.

The detergent spheres of the invention have a unique combination of both physical and chemical properties. As stated above, they are transparent, stable, non-adhesive and free flowing and exhibit excellent washability during a laundry washing process, and have excellent dissolution properties, especially in the washing machine, and generally have low hygroscopicity so that they are not appreciably affected when is in a humid environment (95-100% relative humidity).

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The small balls according to the invention generally have a dirt removal capability which is comparable to if not superior to currently used laundry detergents. The washing or cleaning ability is appropriately measured by the standard tergotometer test (U.S. Testing Company, Hoboken, New Jersey, U.S.A.) and with practical machine washes. In the 5 Tergotometer test, an aqueous solution of the detergent (0, ΙΟ, 5% concentration) is stirred with contaminated cloth samples (and usually with clean cloth samples also for reapplication efficiency) and the washing performance is then appropriately determined by "before" and "after" readings on a color difference meter (e.g. Gardner o Color Difference Meter). The test can be carried out at any temperature (generally room temperature for boiling) with stirring from 0-250 rpm. per minute for 5-20 minutes (conveniently 10 minutes) at water hardnesses from 0 to 300 ppm or more (such as CaCO3). Before the "after" readings, the cleaned cloth samples are rinsed a few minutes in water of the same hardness as used during the washing step, dried and evaluated.

The dissolution rate of the beads according to the invention is measured in water from room temperature to the boiling point (generally and conveniently at 0 40 ° C). The process generally consists of adding 2 g of the product to 500 ml of water at a selected temperature and stirring under selected standard conditions until all the product has dissolved. Specifically, the procedure consists of using a 600 ml beaker, 12 cm high and 8.5 cm in diameter (very flat bottom) and marked for: 5 every 50 ml. Place 500 ml of water in the beaker, adjust the temperature, add 2 g of the product and stir. Stirring is carried out by means of a magnetic stirrer, which is a cylindrical rod with a 1 mm plastic coating. The total dimensions of the rod are 12 mm in diameter and 6.2 mm in length. The rotational speed is set to obtain a vortex whose tip lies at the 300 ml graduation of the beaker.

The small beads of the invention, when measured as described above, have dissolution rates from § to 5 minutes at 40 ° C.

, J. The penetration hardness of the beads of the invention can be measured by the ASTM method D217-52T (Richardsom method). Values obtained for the matrix products of the invention range from approx.

40 to 75 (tenths of a millimeter).

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Product stickiness (including spreading and transferability by rubbing) is determined by rubbing, under a 2 kg weight, of e-shaped 1 "cylinder of the product on a standard cotton cloth (10 cm long) and measuring the amount of product released by friction when the cloth is pulled under the weight-loaded cylinder. P 5 items have friction values (transfer factors) of approximately <50 mg to 200 mg of product per 10 cm strip of cotton cloth. Preferred products have transfer factors of <50 mg to about 100 mg. .

The product transparency is appropriately measured by means of a lamp / fo 10 cell / galvanometer system, the percentage of transmitted light being read after a zero setting. Spectro-colorimeters can also use Mainly total transparency (i.e.> 95%) can be achieved with products of the invention.

Other relevant parameters for the pellets of the invention are the solidification temperature (S.P.) and their viscosity in the fluid state, since these are important factors in their processing, especially to the shaped shapes described hereinbefore. These parameters have a direct effect on the production rate, size and handling of such shaped product shapes (e.g. small balls) and also affect the transparency, tackiness and flowability of the final product. The solidification temperature of the detergent spherical balls of the invention generally ranges from 40 ° C to 100 ° C, and the viscosity, measured by a dropping sphere viscosimeter, may range from approx. 50 cps to 3000 cps, the most suitable values being in the range of approx. 1000 to approx. 2000 cps.

3Q Subject to the restrictions set out below, the fatty acids used in the preparation of the soaps in component A may contain approx. 6 to 22 or more, preferably approx. 8 to 18 carbon atoms, and be of animal, vegetable, mineral or synthetic 35

6 DK 155749B

origin, and they may be saturated or unsaturated hydrocarbon carboxyl = straight, mono- or poly-branched chain acids. Examples of such acids alone include capric acid, caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, oleic acid, elaidic acid, isostearic acid, palmitic acid, undecylenic acid, tridecylenic acid, penta = decylenic acid, 2-lower alkyl acids ( -methyltride = canoic acid, 2-methylpentadecanoic acid or 2-methylheptadecanoic acid) or other saturated or unsaturated fatty acids. Dicarboxylic acids may also be used, such as dimerized linolenic acid. Other higher molecular weight acids such as rosin or tallow oleic acids, e.g. abietic acid, * can be used.

In order to obtain optimum solubility, hardness, viscosity, melting and solidification properties, mixtures or mixtures of the above and other types of fatty acids containing at most approx.

> 1050 fatty acids containing more than 18 carbon atoms and preferably at least approx. 5%, but no more than approx. 70%, fatty acids with 18 carbon atoms. A preferred class of fatty acid mixtures may e.g. contain approx. 0-5% C8-, 0-10% C1-, 0-30% C12-, 0-20% Cl4-, 10-50% Cl6- and 5-70% C3 -saturated fatty acids. Easily available commercially available mixtures as well as 3 mixtures of such mixtures to obtain the most suitable distribution of fatty acids which can be used include distilled palm and palm kernel fatty acids, distilled coconut oil fatty acids, hydrogenated tallow fatty acids and commercially available stearic acid. The fatty acid content in parts by weight of several such mixtures and mixtures thereof is illustrated in the following table:

TABLE A

ABCDEFGH 3 C8 - 4.0 - 2.0 - 2.0 1.3 2.7 C10 - 3.0 8.6 1.5 - 1.5 1.0 2.0 C12 - 45.0 66.2 22.5 - 22.5 5.0 30.1 C 4 5.0 19.0 25.0 11.0 - 9.5 8.3 13.7 3 Cl6 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

Max.

unsaturated. 2.0 12.0 - 7.0 4.0 8.0 5.0 8.7 - - -> -i - - - I_ »- - I _ _ I - ----

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In the above table, mixture A = commercially hydrogenated tallow fatty acids "B = commercial distilled coconut oil fatty acids" C = commercial synthetic fatty acids 5 "D = 1: 1 mixture of A and B (preferred)" E = commercial stearic acid

"F = 1: 1 mixture of B and E

"G = 2: 1 mixture of A and B

"H = 1: 2 mixture of A and B.

1 0

For the in situ saponification of these fatty acids, any alkali metal, alkaline earth, imeta1, ammonium or amine salt forming base, such as, for example, can be used. sodium, potassium, magnesium or ammonium hydroxides, mono-di or triethanol-15 or propano-1 am in there or any other such base which results in a water-soluble salt or soap of the fatty acid which is saponified. The base is preferably in the form of a concentrated aqueous solution, e.g. with approx. 20 to 49% concentration, and at approx. the temperature of the molten fatty acid when mixed therewith. An approximately stoichiometric amount of base is preferably used unless a product containing small amounts of excess fatty acid or base is desired.

Component A soap, apart from its known washing function, gives the small balls of the invention body, hardness and non-adhesive properties. Use of more than approx. However, about 50% of component A for the preparation of the detergent target balls according to the invention increases the melting or fluidization temperature (to about 110 ° C or more), the viscosity of the hot melted liquid and the solidification rate thereof too much, the manufacturing process is prevented and there is a tendency to unreasonably reduce the transparency and dissolution rate of the resulting beads. Use of less than approx. 15-20% of Component A, on the other hand, reduces the viscosity of the hot, molten liquid and its rate of solidification too much, in addition to obtaining pellets which are too soft and sticky at any ratio of Components B to C.

Generally, it is preferred to use the fatty acid soap component A in: of the alkali metal salts such as potassium and more preferably sodium salt

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or "mixtures thereof. An excessive amount of potassium soaps has been found to result in products which are too opaque and soft, and hence no more than about 25% of component A soaps should be potassium soaps. Preferably at least about 50% and up to 100% of component A be 5 sodium soaps.

The composition of the pellets of the invention may contain approx. 15-50%, preferably approx. 20-45% and most advantageously approx. 25-35% of component A, preferably at least approx. 40% is alkali = 3 metal salts of hydrogenated tallow fatty acids, and preferably at least approx. 35% are alkali metal salts of distilled coconut oil fatty acids.

As component B, virtually any soluble synthetic organic detergent, or mixtures thereof, of the type 5 anionic sulfonate and sulfate and of the nonionic aliphatic type may be used, suitable descriptions of which can be found in McCutcheons's "Detergents and Emulsifiers" , 1969 Annual, and in "Surface Active Agents" by Schwartz, Perry and Berch, Volume II, 1958 (Interscience Publishers), the disclosures of which are incorporated herein by reference thereto.

0

Suitable anionic water-soluble detergents include the alkyl aryl sulfonates, especially the higher alkyl (10-20 carbon atoms) benzenesulfonate salts, preferably linear alkyl benzene sulfonates, wherein the alkyl group contains 10-16 carbon atoms. The alkyl group is preferably linear, and especially those groups having average alkyl chain lengths from 11 to 13 or 14 carbon atoms, such as the linear dodecylbenzenesulfonate salts.

Preferably, the alkyl benzene sulfonate also has a high content of meta-isomers and a correspondingly low content (somewhat below 50%) of the ortho and para isomers. One such suitable detergent type is disclosed in U.S. Patent No. 3,320,174.

Typical examples of useful anionic detergents are also olefin = 5 sulfonate salts. They generally contain long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (with the OH group located at a carbon atom not directly attached to the carbon atom bearing the -SO 2 group). More commonly, the olefin sulfonate detergent comprises a mixture of these two compound types in varying amounts, often in association with long chain disulfonates or sulfate sulfonates.

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Such olefin sulfonates are disclosed in many patents, such as U.S. Patent Nos. 2,061,618, 3,409,637, 3,332,880, 3,420. 875, 3,428,654 and 3 * 506,580, and in British Patent Specification No. 1,139,158, and in the article by Baumann et al in Fette-Seifen-Anstrichmil tel. 4, at pages 247-253 (1970). All of the above mentioned literature sites are incorporated herein by reference thereto. As stated in these patents and in the published literature, the olefin sulfonates can be prepared from straight-chain α-olefins, inner olefin * olefins, wherein the unsaturation is found in a vinylidene side chain (e.g. dimers of α-olefin), etc., and more commonly mixtures of such compounds, wherein the α-olefin is usually the major constituent. The sulfonation is usually carried out with sulfur trioxide under low partial pressure, e.g. SO ·, which is strongly diluted with inert gas, such as air or nitrogen, or under vacuum. This reaction generally results in an alkenylsulfonic acid, often with a sultone. The resulting acidic material is then generally made alkaline and treated to open the sultone ring to form the corresponding hydroxyalkanesulfonate and / or alkenyl sulfonate. The number of carbon atoms * in the olefin is usually in the range of about 10 to about 25, more usually from 12 to 20, for example, a mixture of mainly 20 0 - 2 and C 2 g having an average of about 14 carbon atoms, or a mixture of mainly C of about 16 carbon atoms.

Another class of water-soluble, synthetic, organic, anionic detergents include the higher (10 to 20 carbon atoms) paraffin sulfonates. These may be the primary paraffin sulfonates produced by reaction of long chain α-olefins with bisulfite, e.g. sodium bisulfite, or paraffin sulfonates having the sulfonate groups distributed along the paraffin chain, such as the products produced by the reaction of a long-chain paraffin with sulfur dioxide and oxygen under ultraviolet light followed by neutralization with NaOH or another suitable base (as in US Pat. 2,503,280, 2,507,088, 3,260,741 and 3,372,188 and German Patent No. 735,096). The hydrocarbon substituent in the paraffin sulfonate preferably contains about 13 ti. ' 35 carbon atoms and the paraffin sulfonate will normally be a monosulfate, but may, if desired, be a di-, tri- or higher sulfonate. A paraffin disulfate can typically be used in admixture with the corresponding monosulfonate, e.g. as a mixture of mono- and di-sulfonates containing up to ca. 30% of the disulfonate.

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DK 155749B

The hydrocarbon substituent in the paraffin sulfonate will usually be linear, but branched chain paraffin sulfonates can also be used. The paraffin sulfonate used may be sulfonated at the ends, or the sulfonate substituent may be attached to 2-carbon atoms or another carbon atom in the chain. Similarly, any di- or higher sulfonate used may have the sulfonate groups distributed over different carbon atoms in the hydrocarbon chain.

Additional water-soluble anionic detergents include those of the hay (e.g. C ^ o_2>>) acyl sarcosinates, isethionates and taurides, such as sodium laurylsarcosinate, the oleic acid ester of isethionic acid, and the sodium or potassium N-methyl-N-lauroyl or oleylides . Another type of anionic detergent is a higher alkyl phenol mono and / or disulfonate such as one having an alkyl group having 9-25 carbon = 5 atoms, preferably a linear alkyl group having about 16 to 22 carbon = atoms which can be prepared by sulfonating the corresponding alkyl = phenol to a product containing an excess of 1.6, preferably about 1.8, e.g. 1.8 to 1.9 or 1.95 SO alkylphenol = molecule. In these sulfonates, the phenolic hydroxy group may be blocked, such as by ether or esterification. Thus, the li atom of the phenolic OH group may be replaced by an alkyl group, e.g. an ethyl group, or with a hydroxyalkoxyalkyl group, e.g. a - (CH 2 CH 2) X H group wherein x is 1 or more, such as 5, 6 or 10, and the resulting alcoholic OH group may be esterified to form, for example, a sulfate, e.g. -OSO ^ Na. Yet another type of anionic detergent is CQ220 "a ^ kanoy ^> e.g. coconut oil fatty acid, mono-, di- and tri-glyceride sulfonates.

The synthetic detergent types described above are representative of the anionic organic sulfonates which act as or in the component B.

Other suitable anionic detergents useful as or in component B are the anionic organic alcohol sulfates, i.e.

55 sulfate esters of an OH group-containing hydrophobic or oleophilic moiety, such as the C lauryl and tallow alcohol sulphates, α- and α-methoxyoctadecyl sulphate, C 2 O 2 alkanoyl (coconut oil fatty acid) mono- and di-glyceride sulphates and higher alkyl (C 2 O 2) phenol sulphates.

Further suitable anionic detergents useful as or in

n DK 155749B

component B, are the ether sulfates which are sulfate esters of non-ionic detergents, i.e. reaction products of ca. 1 to 20 moles of a C ^^ alkyl alkyl alkylene oxide, preferably ethyleneside, with 1 mole of a Cg₂ ^ reactive hydrogen-containing aliphatic or alicyclic compound including aliphatic and alicyclic alcohols such as lauryl, tallow, oxotridecyl, coconut oil and abietyl alcohols , aliphatic dihydric alcohols such as polyoxypropylene ethylene and propylene glycol diamines, and dithiols, aliphatic and alicyclic carboxylic acids such as stearic acid, arucic acid and abietic acid, aliphatic mercaptans such as dodecyl mercaptan, aliphatic and alicyclic aliphatic and alicyclic amides, such as stearylamide or with 1 mole of a Cg 2 0-reactive hydrogen-containing aromatic compound including alkyl phenols such as nonyl and dinonyl phenol.

Although the above-mentioned structural types of anionic, organic sulfates and sulfonates are generally preferred, it will be appreciated that the corresponding organic phosphates (see, e.g., U.S. Patent No. 3,595,968) and phosphonates are also useful anionic detergents: component B.

In general, the anionic detergents are preferably salts of alkali metals, such as potassium and especially sodium, although salts of ammonia cations and substituted ammonium cations derived from lower (2 to 4 carbon atoms) alkanolamines, e.g. triethanolamine, tripropanolam and diethanol monopropanolamine, and of lower (1 to 4 carbon atoms) of 25 chylamines, e.g. methylamine, ethylamine, sec.-butylamine, dimethylam tripropylamine and tri-isopropylamine may also be used.

The aliphatic nonionic detergents acting as or in component B can be described as reaction products of ca. 2 to 50 moles of a C₂ _ alkyl alkylene oxide, preferably ethylene oxide, with 1 mole of a

Cg_24-reactive hydrogen-containing aliphatic compound, examples; such are the reactive hydrogen-containing compounds, hereinafter referred to as precursors of sulfate esters of the nonionic aliphatic gene.

35

Preferred nonionic detergents are those having the formula:

R0 (C2H40) nH

wherein R represents the rest of a saturated, straight-chain or branched all

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fatty alcohol, preferably a primary alcohol of approx. 8 to 20, preferably approx. 12 to 18 carbon atoms, and n is an integer from ca.

2 to approx. 50, preferably from ca. 3 to approx. 20th

Typical commercially available nonionic detergents suitable for use in the detergent of the invention include an ethoxylated product having an average of 11 ethylene oxide units (EO units), a fatty alcohol having a carbon chain of 14-15 carbon atoms. a fatty alcohol having 12-15 carbon atoms in the carbon chain, which fatty alcohol is ethoxylated with an average of 7 EO units, an alkanol of 10 16-18 carbon atoms ethoxylated with an average of 10 to 11 EO units, and the reaction products of an average of 11 moles of EO with 1 mole of a primary alkanol, of 5 moles of E.O. with 1 mole of one

Cg_11 primary alkanol and of 7 moles of E.O. with 1 mole of a C 12 O 3 primary alkanol and 3: 1-1: 3 mixtures of the reaction product of 20-50 moles of 15 E.O. with 1 mole of a C-j- primary alkanol and of 3-5 moles of E.O. with 1 mole of a Cg_ Q primary alkanol. It will be appreciated that in the event that a compound is indicated as containing a range of carbon atoms, it is in fact present as one compound or mixture of compounds, each containing a number of carbon atoms within such range. The indicated E.O. values are similarly averaged.

Other suitable nonionic aliphatic detergents include the liquid and semi-solid reaction products of ca. 3-20 moles of E.O. with 1 mole of 25 O-1 (-secondary alkanols, the reaction products of about 5-7 moles of EO with 1 mole of C 1-6 g alkanediols, and "Pluronics" including the reaction products of about 2-20 moles of EO with polyoxypropylene ethylene and propylene glycols, diamines and dithiols of higher molecular weight (eg at least about 150).

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As noted above, mixtures of the aforementioned detergents can be used as component B. A preferred embodiment consists in the use of at least about 10%. 50%, preferably approx. 65 and up to 100% of a nonionic aliphatic detergent, especially the nonionic reaction product of about 35%. 2 to 50, preferably approx. 5 to 15 moles, ethylene oxide with 1 mole of a saturated aliphatic alcohol, preferably a primary alcohol, of approx.

8 to 20, preferably approx. 11 to 16, carbon atoms, as or in component B, any residue being an anionic, organic sulfonate or sulfate detergent. According to another embodiment, the component 13

DK 155749B

ten B at least approx. 30% and up to 100% of an anionic organic ether = sulfate detergent. Examples of such embodiments include those in which component B contains substantially 100% of the nonionic aliphatic detergent such as the one immediately described above, or ca. 70% of such a nonionic detergent and approx. 30% 5 of the anionic detergent such as an alkyl aryl sulfonate salt, especially sodium dodecylbenzenesulfonate, or substantially 100% of the anionic ether sulfate detergent such as sodium lauryl polyethyleneoxy (2-9) sulf

The component B detergents contribute to improved solubility in hard water and to provide improved pulp compositions and pellets according to the invention, especially in hard water, and / or with respect to synthetic fiber materials such as nylon, polyesters such as Dacron, and polyacrylonitriles. such as Orlon and Acrilan. They also increase the water solubility and velocities at which such compositions and spheres are wetted and dissolved, but should generally not exceed <ca. 65%, preferably no more than approx. 55% of the basis for avoiding the formation of increasingly softer stickier and more hygroscopic and less transparent products. Component B should contain a small amount or no mineral salt 20 which is a very common component of commercially available detergent compositions for the purpose of avoiding harmful effects: on the transparency properties of the pulp products and can be used in the pulp compositions and pellets in quantities going from approx. 10 to approx. 65%> preferably from approx. 20 to c; About 55%, most preferably from approx. 30 to approx. 45% by weight.

A greater amount (% 50%) and preferably from 75 to 100% of the component C solvent should normally be liquid, i.e. with a solidification point (S.P.) below ca. 40 ° C, preferably below room temperature, 30 and a boiling point of at least approx. 100 ° C, preferably at least approx. 120 ° C to approx. 400 ° C. It should be essentially non-volatile and have a negligible vapor pressure at room temperature and cause negligible losses on evaporation by aging or storage. Particularly good, i.e. 1. volatility, is thus indicated by a weight loss of 5% or less after 35 hours for 2 hours at 105 ° C or after 10 hours at 43 ° C for a 20 g sample of the solvent in a container having an evaporation surface of approx.

p 46.5 cm placed in an oven through which an air flow passes] Of the said non-volatile part of said component C, at least approx.

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10% be a divalent alcohol to obtain 10% thereof in component C and preferably at least 25% and up to 100%. One or more substantially water-insoluble organic solvents, such as benzyl alcohol, may form part of the non-volatile portion in an amount not exceeding, among others. 90%, preferably at most approx. 75% and most preferably not for more than approx. 50% by weight of said fraction.

A particularly suitable water-soluble organic solvent is propylene = glycol. The ratio of water-insoluble to water-soluble solvents in component C is preferably in the range of from approx. 1:10) to 10: 1, preferably from ca. 5: 1 to approx. 1:10 and most preferably from 1: 1 to 1:10. Other very preferred ratios are from 1: 2 to 1:10 and from 1: 4 to 1:10.

For the purposes of the invention, and solely as a general guideline,> a solvent may be considered water-insoluble if its solubility in water at 20 ° C is less than 10% by weight and preferably less than about 10% by weight. 5% by weight. Benzyl alcohol, which is one of the preferred water-insoluble solvents, has a stated solubility of 4 g / ml. 100 ml of water at 17 ° C.

)

As a suitable, substantially water-insoluble organic solvent, benzyl alcohol or lauryl alcohol or terpineol is preferred, but as examples of other such solvents which can be used in or as component C, as a rule of thumb there may be mentioned any such liquid solvents which are more water-insoluble than benzyl alcohol, generally including any substantially water-insoluble aliphatic, alicyclic or aromatic liquid hydrocarbon, halogenated (iodine, bromine or preferably chlorine) hydrocarbon, hydroxylated hydrocarbon, ether, ester or the like, having the above-described properties, eg. octane, hexadecane, chlorine = hexane, chloro and dichlorobenzene, heptyl, oxotridecyl and hexadecyl = alcohols, abietyl alcohol, octanediol, phenethyl alcohol, mono- and di-C1-4 alkylphenols, phenyl ether, benzyl ether, 1,2-dibutoxybenzene, 2 -benzyloxyethanol, butyl ether, diethyl and dibutyl phthalates, benzyl = propionate, isopropyl myristate, palmitate and stearate, and the like.

Similarly, as a rule of thumb, the substantially water-soluble solvent in or as component C may be any such solvent which is more water-soluble than benzyl alcohol.

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It may be of any chemical type, but is generally a monovalent or polyhydric alcohol, etheric alcohol or amine such as the 1,7-heptane = diol, the mono- and polyethylene and -propylene glycols having a molecular wall of up to approx. 4000, and the mono-Cj ^ alkyl ethers thereof, sorbitol, glycerol, glucose, diglycerol, sucrose, lactose, dextrose, 2-pentanol, 1-5 butanol, mono-, di- and triethanolamine, 2-amino-1-butanol and the like especially the polyhydric alcohols and alkanolamines.

The solvent component C is essential for the preparation of molten spheres that are transparent and further serve as a unifying or common solvent for component A soap and its fat precursor as well as for component B detergent. It further fluidizes the melt and facilitates its shaping into small balls which solidify rapidly upon cooling. It further increases the solubility of the small-ball products. Essentially water-soluble solvents 15 of component C are good common or unifying solvents for components A and B as well as good water solubilizers for the pellets, but they tend to increase the softness, tackiness and hygroscopicity thereof, especially the solvents of the polyvalent alcohol type, below. storage and use. Such trends are controlled by the invention by limiting the amounts of water-soluble solvents and by using water-insoluble solvents in component C as described above. The water-insoluble solvent, and especially benzyl all alcohol, is also unique in terms of the body and shape stability of the detergent target balls of the invention. However, it should be noted that a controlled degree of hygroscopicity of the beads may be beneficial in preventing products made therefrom from drying, shrinking and cracking during storage and use. Of course, component C, like component B, should also be stable or resistant to the action of basic or alkaline material used in the production of component A soap in situ.

Component C should generally not exceed approx. 65%, preferably 35 not more than approx. A-5% and most preferably no more than approx. 25% of the composition of the pellets according to the invention in order to avoid unreasonably reducing the cleaning properties thereof as a result of the resulting smaller amounts of components A and B and in order to avoid excessive increase of the sweat.

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gene (fluid leakage), hygroscopicity, softness and stickiness of the small spheres. In general, the composition of the beads of the invention should contain approximately 10 to 45, preferably 10 to 35, and most preferably 10 to 30% by weight of component C.

5 Particularly preferred amounts consist in the use of ca. 1 to 2 parts by weight of component A, 1 to 4 parts by weight of component B, and 1 part by weight of component C in small sphere compositions of the invention, other than water component D.

The water component D contributes to lowering the viscosity of the present materials in liquid or molten state and facilitates neutralization of the fatty acid precursors of component A soaps in the process of making the pellets according to the invention, in addition to contributing to solubilization of components A 15 and B Also, if not all of the water is suitably introduced in the form of an aqueous solution of the base or alkaline material used in the in situ neutralization or saponification of fatty acid for the runners of component A soap. Water also increases the water solubility and transparency of the pellets of the invention, and as a result of the partial loss thereof from the pellets by evaporation during aging and storage, especially from the outer layers of the pellets, it reduces the surface tackiness and increases their hardness. Too low a quantity of water adversely affects the workability of the present compositions and the transparency of the resulting small balls. An excess of 25 high water reduces the solidification rate of these pellets too much and increases their tackiness and softness too much.

In general, the materials and beads of the invention should contain about 30 1 to 35 parts by weight, preferably 5 to 25 parts by weight and most preferably 10 to 15 parts by weight of the water component D per unit weight. 100 parts by weight of (A), (B) and (C) and generally not more than approx. 15% by weight of component D in the matrix.

In the process of making the detergent goblets of the invention, it is preferred to melt the free fatty acids corresponding to the soaps of component A in a heated container, mixing components B and C and gently stirring the mixture at a temperature above, but preferably at most, approx. 50 ° C above the melting point of the free 17

DK 155749B

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 said homogeneous liquid, is then mixed therein, preferably gradually and / or in small amounts, in order to avoid lumps and superheating, until in situ neutralization and / or soaping. The addition of the fatty acids in said liquid is complete. An approximately stoichiometric amount of the base is conveniently used to avoid excess base or fatty acids in the product. Neutrality of the product can be ascertained by e.g. periodic testing with phenol = phthalein indicator. If desired, the detergent component B can first be dissolved in the heated solvent component C and the resulting solution may be filtered to remove mineral salts and other undissolved material before the B and C components in the form of the resulting hot, clear solution are mixed into the molten fatty acids.

After all the base has been added and the resulting hot liquid product has been sufficiently mixed until it is established that the fatty acids are neutralized, any desired small amount of known detergent additives can be mixed, if desired, with any further desired amounts of water component D. Alternatively, some of the water component D may be added together with the detergent component B and / or the solvent component C.

In some cases, it may be desirable and within the scope of the invention to replace up to approx. 75% or more of the initial free fatty acids are melted with their corresponding soaps or salts, e.g. pure soap or kettle soap, which of course occurs in conjunction with a corresponding reduction in the amount of soap or salt-forming base which is then blended into the hot melt to neutralize or saponify the free fatty acids therein.

When a product containing a heat sensitive, anionic sulfonate or sulfate detergent is prepared as or in component B, such a detergent is preferably not mixed with the molten fatty acids prior to its exothermic neutralization reaction with the base but then mixed instead of or with the previously neutralized cooled liquid (to just above the solidification point of said liquid containing the soap or fatty acid salt component A, the solvent component C and any non-ionic aliphatic detergent amount of the component B).

1 8

DK 155749B

The hot liquid material for making the pellets of the invention, prepared as described above, can, if desired, be cooled and solidified together or otherwise desired. Preferably, such cooled and solidified material is re-melted or, more preferably, said hot, liquid material 5 is used without such intermediate cooling, solidifying and re-melting steps and / or evaporation and is used to prepare transparent, water-soluble, non-adhesive and essentially non-hygroscopy detergent goblets.

1 o

An appropriate method of making the beads may include the use of equipment (i.e., tubes, funnel-shaped food containers, containers, nozzles, valves, etc.) equipped with suitable heaters effective for maintaining the temperature of the hot or molten liquid material. according to the invention just above its solidification point (ie, from about 20 ° C up to about 50 ° C, preferably up to about 20 ° C, above said solidification point), until the formation of said droplets falling from an appropriate opening or appropriate openings. Such solidification points can range from as little as approx. 40 ° C and until approx. 100-110 ° C. If such a temperature is allowed to fall to or below such a solidification point, premature solidification will apparently begin before the desired droplet and ball formation. The flow of hot liquid material into and through the openings will thereby be diminished, made difficult or brought to a complete halt.

25

If such a temperature is too high, loss of some amount of the components, with consequent changes in the desired optimum conditions or amounts, may occur as a result of decomposition and / or evaporation or the like, and any accompanying adverse effects on composition and ball characteristics, such as pelletizability (solidification speed, etc.), viscosity, transparency, hardness, solubility, purity and / or hygroscopicity and the like. Excessive loss of volatile components at such high temperatures may further result in premature solidification of the soap component A and / or the detergent component B in the equipment prior to droplet and ball formation. Furthermore, if the temperature of the liquid material in the droplets formed at said apertures is too high, solidification during ball formation on said support below the apertures will be prevented and the still fully liquid droplets will hit the support and spread or forming a flat, continuous film thereon.

The viscosity of the hot liquid detergent material is also an important factor, especially in determining the exit rate (rate of the droplet formation) and the size of the droplets. Such viscosities can be measured with a "falling ball viscometer" ranging from approx.

50 to approx. 3000 cps, preferably from approx. 1000 to approx. 2000 cps, and is an inherent property of the materials for the manufacture of the small spheres of the invention.

The size of the openings, the temperature, the viscosity and the rate of solidification of the material in the droplets as well as the vertical distance between the openings and the support and the temperature of the support and the atmosphere between the openings and the support are consequently independent variables to be controlled to achieve the desired formation. of small balls which can vary in size (maximum dimension) from approx. 2 to approx. 9 mm, preferably from approx. 3 to approx. 5 mm, and having the shape of a disk or plate, ball, bean or lens, toe-drop or a cut-off version thereof or the like.

In general, there should preferably be several openings, e.g. up to 500 or more, each of which can range from approx. 0.5 to approx. 4 mm in diameter, at the bottom of the container, which is preferably equipped with agitators and contains the hot liquid detergent. The height between the openings and the molding can be from approx. 0.5 to 5 cm, preferably from ca. 1 to 2 cm. The openings or nozzles and / or container may be provided with vibration means which preferably vibrate in the vertical direction, in order to facilitate separation of the droplets from and prevent formation of stalactites thereon. Such vibration means may e.g. vibrate at a frequency of approx. 0.2 to 5 cycles per 30 and preferably with an amplitude such that contact between the support and the drop is produced when it is formed.

It may be convenient to provide the support with vibrating means, thereby further acting to prevent the attachment of the small balls to the support and to facilitate their removal from the support. The support, which is preferably moving, is made of thermally conductive material, preferably metal, such as a rotating cylinder, or more preferably as an endless, movable metal band equipped with means for continuously removing the balls, such as angular knife scrapers, and

20 DK 1557 4 9 B

it may also optionally be provided with additional vertically or horizontally inclined vibration means to prevent adhesion of the beads to the support as well as to facilitate their removal. Such support may in fact serve a variety of containers which continuously deposit droplet-forming droplets thereon. Of course, the temperature of the support and the atmosphere through which the droplets fall should be somewhat below the solidification point of the hot liquid detergent such that at least a substantial portion of each droplet substantially solidifies at or before contact with the support at any particular composition, temperature thereof, droplet size and height between opening and support. The underside of the support can e.g. cool by means of an air blower or by means of a cooling liquid spray.

Preferably, the beads collected by the method described above should age in warm, dry air prior to packaging in order to promote hardness and obtain freedom of stickiness.

It will be appreciated, of course, that transparent detergent balls of the present invention may also be prepared by methods other than those described above, and that they may be given any other shape or design such as cylindrical, cube pyrimidal, tapered, etc.

The following examples are not limiting, but only examples of preferred embodiments of the invention. All quantities and ratios disclosed herein and in the appended claims are by weight and weight ratios, unless otherwise stated.

Example 1 and the other examples in Table II list and describe, in connection with Table I, component ingredients and quantities thereof which are used to prepare materials and spheres to serve as examples of the various features of the invention. In preparing such materials, component A's fatty acids are melted in a heated container, solvent component C is poured, detergent component B is admixed, and the mass is heated with gentle stirring at a temperature of not more than 50 ° C, generally no more than ca. 20 ° C and usually approx. 2 to 10 ° C above the melting point of said fatty acids until a homogeneous liquid is obtained. Such temperatures may range from approx. 60 to approx. 110 ° C, generally from ca. 70 to 100 ° C and usually from ca. 80 to 90 ° c. The water component D containing 21

DK 155749B

solved an approximate stoichiometric amount of caustic soda, which has approx. the temperature of the hot homogeneous liquid is then gradually incorporated therein to avoid lumps and superheating until complete neutralization and / or until the saponification of the fatty acids is completed. Termination can be ascertained by periodic testing with phenol = 5 phthalein indicator or by adding a few drops of such indicator to the warm, homogeneous liquid and observe if a pink hue develops. In preparing compositions using heat sensitive, anionic, sulfonated detergents and / or sulfate detergents in component B, such detergents can instead be added to the heated container only after neutralization with the caustic soda and the feeling of the neutralized liquid to ca.

1-5 ° C above its solidification point to minimize thermal decomposition of the heat sensitive anionic detergent.

If the heated container in which the mixing and neutralization is carried out is not formed with apertures as described below, the resultant hot liquid materials of the invention, while maintaining their temperature above their solidification point, are transferred to a heated container, the bottom of which is there are several openings or nozzles with adjustable openings, which range from approx. 0.5 to approx. 2 mm in diameter, usually approx. 1 mm. The hot, liquid droplets formed at the outlet of the nozzles fall at a distance of approx. 1 to 2 cm through an atmosphere at a temperature below the solidification point of the material down to an endless moving metal band provided with vertical vibrating means and cooled to something below (up to 20-30 ° C below). Solidification of the droplets begins when they are separated from the nozzles, and it is at least partially completed at or before their contact with the tape, so that the pellets at a maximum dimension of on average approx. 2-9 mm, usually approx.

5-5 mm, formed. At a suitable distance from the nozzles, angular knife scrapers remove the fully solidified small balls from the tape and guide them into a container or conveyor for aging, packaging, etc.

All the compositions and beads of the Examples of Table II have acceptable, good or excellent properties in terms of hot melt viscosity, pelletizability, transparency, hardness, dissolution rate (extent of water solubility), hygroscopicity and purity.

22 DK 155749B

TABLE I - COMPONENTS COMPONENT A

Al Hydrogenated tallow fatty acids 5 A2 Distilled coconut oil fatty acids A3 Distilled tallow fatty acids A4 C - ^^ - synthetic fatty acids A5 022 - ^^ acid is A6 Commercial candles 10 A7 Pure soap (15:85 A2 soap: A3 soap + 33% ° water)

COMPONENT B

B1 Non-ionic reaction product of 1 mole of C 11 moles of ethylene oxide (+ 11 E.O.) 15 B2 Non-ionic C 1-6 primary alkanols + 11 E.O.

B3 Non-ionic C ^ 2_i5 ~ Primary alkanols + 7 E.O.

B4 Nonionic C ^^^ - Primary alkanols + 5 E.O.

B6 Non-ionic C -, (- secondary alkanol + 3 E.O.

lp B7 Non-ionic C 1-6 alkanediol (omega omega) + 5 E.O.

20 B8 Anionic sodium (synthesis dodecyl) alkylbenzene sulfonate B9 Anionic nairium sulfate of lauryl alcohol + 3 E.O.

BIO Anionic Sodium C - ^^ _ - Paraffin Sulfonate Car Anionic Sodium Lauryl Sulfate

COMPONENT C

25

Cl Benzyl alcohol C2 Lauryl alcohol C3 Terpineol C4 Diethyl phthalate C5 Phenethyl alcohol C6 Propylene glycol C7 Monoethylene glyco1 C8 Diethylene glycol C9 Triethylene glycol CIO Polyethylene glycol E200

Cll Triethanolamine

COMPONENT D

Dl 33% aqueous caustic solution D2 Deionized water AO D3 4g ^ aqueous solution of caustic soda

TV, C AO / ------ 3_ · _ 1. · 1. -1, · 1 3, JJ

23

DK 155749B

ADDITIONS E

El Optical dye, e.g.

E2 Dye, e.g. Pigmasol Blue 5G

E3 Perfume 5 TABLE II - Examples

Components - parts by weight

Example_A_B_C_D_additions 1 11.0 Al 45.2 Bl 11.4 Cl 10.5 Dl 11.0 A2 11.4 C6 7.0 D2 2 14.0 Al 42.0 Bl 12.0 Cl 10.2 Dl 0.1 El 8 , 0 A2 12.0 C6 5.0 D2 0.004 E2 3 11.0 Al 35.2 Bl 11.4 Cl 10.5 Dl 11.0 A2 10.0 B8 11.4 C6 7.5 D2 15 4 15.0 Al 30.0 B1 11.5 Cl 14.4 Dl 0.25 E1 15.0 A2 7.0 B4 1.5 C6 10.0 D2 0.004 E2 10.0 C11 5 11.0 Al 45.2 B9 15.0 Cl 10 , 0 Dl 11.0 A2 11.4 C6 on 6 11.0 Al 40.0 B1 12.5 Cl 10.0 Dl 0.25 E1 11.0 A2 5.0 B4 12.5 C6 4.15 D2 0.003 M2 0.30 E3 7 15.0 Al 10.0 B1 20.0 Cl 17.1 Dl 0.005 E2 20.0 A2 20.0 C6 10.0 D2 8 11.0 Al 45.2 B2 11.4 Cl 10.5 Dl 11.0 A2 11.4 C6 6.0 D2 9 15.0 Al 20.0 B1.0 Cl 14.4 Dl 0.25 E1 15.0 A2 10.0 B4 5.0 Cll 10.0 D2 0.003 E2 10.0 B7 0.350 E3 10 14.0 Al 25.0 B1 17.5 Cl 13.4 Dl 0.25 E1 14.0 A2 17.5 C6 8.0 D2 0.004 E2 0.30 E3 11 14.0 Al 40, 0 B1 6.0 Cl 13.4 Dl 0.25 E1 14.0 A2 6.0 C2 8.0 D2 0.003 E2 6.0 C6 0.30 E3 6.0 C8 35 12 14.0 Al 40.0 B2 6.0 Cl 13, 4 Dl 0.25 E 14.0 A2 6.0 C4 8.0 D2 0.004 E2 6.0 C6 0.35 E3

6.0 CIO

13 14.0 Al 40.2 B2 6.0 Cl 13.4 Dl 0.25 E1 14.0 A2 6.0 C2 8.0 D2 0.004 E2 ao 4.0 C7 0.30 E3

DK 155749B

24 TABLE II - Examples (continued)

Components - parts by weight

Example_A_B_C_D_Additions 14 14.0 Al 40.0 B1 6.0 C2 13.4 Dl 0.25 E1 14.0 A2 6.0 C3 8.0 D2 0.004 E2 5 12.0 C6 0.30 E3 15.0 Al 40, 0 B2 12.0 Cl 12.0 Dl 7.0 A4 12.0 C8 7.0 D2 16 14.0 Al 25.0 B9 17.5 Cl 13.4 Dl 14.0 A2 17.5 C6 8.0 D2 1 o 17 7.0 Al 22.5 B2 15.3 Cl 7.0 Dl 7.0 A2 15.3 BIO 15.3 C6 2.0 D2 7.0 A3 18 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 io 19 8.0 Al 13.5 B9 18.4 C1K 8.1 Dl 8.0 A2 13.5 BIO 18.4 C6 8.0 A3 20 25.0 Al 25.0 Bl 15.0 Cl 10.0 Dl 20 21 10.0 Al 7.0 Bl 15.0 Cl 11.3 D3 20.0 A6 7.0 B6 24.0 C6 5.0 D2 22 30 , 0 Al 15.0 Bl 10.0 Cl 8.3 D3 25.0 C6 8.3 D2 23 25.4 Al 21.1 Bl 16.9 Cl 7.0 D3 21.1 C6 8.5 D2 25 24 30.0 A6 15.0 Bl 20.0 Cl 5.0 D2 20.0 C6 10.0 D3 25 13.0 Al 40.0 Bl 12.5 Cl 4.3 Dl 17.0 A7 12.5 C6 30 26 18.8 Al 10 , 0 B8 15.0 Cl 17.9 Dl 18.8 A2 10.0 B9 15.0 C2 27 11.0 Al 35.2 Bl 11.4 Cl 10.5 Dl 11.0 A2 10.0 Car 11.4 C6 7.5 D2 h Similar good results when 2.5 parts of both Cl and C6 in Example 19 are replaced with coconut diethanolam id.

The detergents in the form of the detergent gob balls of the invention, in addition to having the properties described above, are generally also of the low or low foaming type, especially when the detergent B

DK 155749 B

25 is nonionic. The combination of non-ionic detergents and detergent mixtures containing non-ion in substances (with, for example, alkylbenzenesulfonates, olefin sulfonates, paraffin sulfonates, etc. and mixtures thereof) with the higher fatty acid soaps is known to result in a foaming or in fact in many cases, a synergistic low- or low-foaming product which is particularly useful for high-temperature machine washing processes (e.g., higher than 60 ° C until boiling). Non-inorganic substances with optimum cleaning properties and in quantities resulting in acceptable and more than acceptable performance are difficult to manufacture in the form of conventional spray-dried products, and the present originaej.se results in excellent low foaming detergents, especially with high non-ionic content which provides a satisfactory solution to the problem.

15

SAMNLIGNINGSEKSEMPLER

28. When 50 parts B8 are mixed with 50 parts C6 at approx. 100 ° C, the resulting soap-free mixture does not solidify upon cooling to room temperature.

Similar results are obtained when Example 50 is repeated using C1 instead of C6.

30. Similar results are obtained when Example 30 is repeated replacing half of C6 with Cl.

31. Similar results are obtained when Example 32 is repeated using B1 instead of B8.

32. When the procedure of Example 1 is followed while admixing 10 parts of hot D1 into a hot, molten liquid at ca. 70 ° C containing 10 parts Al, 95 parts B1 and 95 parts B6, is the resultant hot liquid containing no solvent component C and too little of the soap component A, viscous when warm, and very soft and opaque, when cooled to room temperature.

DK 155749 B

33. When the procedure of Example 1 is followed while admixing a stoichiometric amount of hot D1 into a hot, molten liquid at ca. 80 ° C containing 70 parts Eel, 65 parts B1 and 63 parts B6, the resulting hot, molten liquid, which contains no solvent component C, is very viscous and airy and is hard but opaque and sticky when it is cooled to room temperature.

Detergents listed in the previous Table II are examples of the transparent detergent goblets of the invention. Although such materials as described above are particularly attractive and exceptionally attractive, especially when in pigmented or colored form, they can also form the basis for detergents of substantially similar physical properties in terms of shape stability, size, shape, free flowing properties, lack of stickiness or stickiness, water solubility and hardness, but with very varying properties with respect to dirt removal, foaming properties, etc., as a result of incorporation in such compositions of detergent balls according to the invention of any of the conventional detergent auxiliaries as well as other components, is described in the following. Among such materials mentioned may be made use of fillers (e.g., silica, bentonite, insoluble silicates, molecular sieve components, etc.), inorganic builders (e.g. bicarbonates, borates, carbonates, phosphates, silicates, etc.). oxidants (e.g., perborates, percarbonates, persulfates, etc.), organic builders (e.g., aminopropyl γ-carboxy ester, such as nitrile lotric acetic acid tri-sodium salt, sodium methylenediaminate tetraacetate, dihydrohydroxy mine in acetate, 1,2-di-aminocyclohexanedacetic acid, polyelectrolytes, phosphonates, citrates, gluconates, clarifiers, UV absorbers, foam regulators (e.g., soaps, polysiloxanes, fatty amines etc. with high molecular weight), foam enhancers ( e.g., amine oxides, fatty acid canola amides, etc.), special surfactants (e.g., cationic, amphoteric and ampholytic), germicides, preservatives, etc.

35

DK 155749 B

27

Additives of the above type can be used in any desired amount to produce the desired functional properties, such components such as preservatives, germicides, dyes, pigments and U.V. absorbents generally being used in minor amounts, e.g. 0.01 weight ^ up. to 10% by weight. Other additives 5 can be used in any amount, e.g. fillers (1-75%), builders (1-85 fo), foam enhancers (1-75%), foam breakers and foam controllers (0.1-20%), sequestering agents (0.1-20%), oxidizing agents ( 1-50%) etc.

Of particular value is the incorporation of builders and additives which may have thermal or other instability caused by the environment. In this regard, the use of U.V. absorbents, clarifiers and foam control agents, especially of the polysiloxane type, is of particular importance.

I 5

Of the inorganic builders which are preferably used, the alkali metal salts (e.g., tripolyphosphate, pyrophosphate, hexametaphosphate, etc.) are suitably used, and of these, sodium tripolyphosphate (anhydrous, hydrated, hexahydrate) is usually the builder of choice, as a result of expense factors.

The detergents in the form of the detergent spheres of the invention, which use the transparent matrix together with any and all of the aforementioned adjuvants, may be uniform in appearance (e.g., transparency), since the matrix itself may be more or less transparent ranging from very transparent to translucent to opaque. In all cases, the translucent and opaque products have a particularly comfortable and special appearance.

0

The following examples illustrate transparent matrix mass combinations with other excipients: 28

DK 155749B

Example 54 65 parts of the material of Example 1 (before pelleting) and while in the fluid state (T = 70 ° C) are thoroughly mixed with 35 parts of anhydrous sodium tripolyphosphate and the material is then pelleted as in Example 1. The resulting beads are free flowing, non-sticky, easily water soluble and have excellent washability properties. The small balls have a dense, opaque white hue and have a very specially polished, white marbled look.

Example 55

Example 1 is repeated while adding 0.2 parts of clarifier (Optiblanc LSN) to the material. The clarifier is first dissolved in the solvent, followed by the procedure similar to Example 1. Excellent transparent pellets are formed.

Example 56

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

Example 37

Example 1 is further repeated except that the solvent consists of only 20 parts of propylene glycol.

Example 58

Example 1 is repeated, further utilizing as the non-ionic material a C c ^ ^1 alcohol ethoxylate containing 11 moles of condensed ethylene oxide.

Example 39 35

Example 1 is further repeated replacing half of the nonionic material with component B3.

DK 155749B

29

The invention has been described with reference to preferred embodiments thereof, and it will be apparent that modifications and variations therein will be apparent to those skilled in the art, which modifications and variations are to be considered as falling within the scope and scope of the invention and the scope of the following claims.

5

Example 40

Example 34 is repeated except that instead of the 35 parts of tripolyphosphate, 35 parts of a type A molecular sieve zeolite as described in German Publication No. 2,412,836 and 2,412,837 published 31 are used. October 1974. The zeolite is specially of the type A100 sodium aluminum silicate containing 20% Κ -, Ο and having a mean particle diameter of 5.9-5.4 microns and a pore size of approx. 4 Angstrom.

15

Example 41

Example 34 is repeated using 35 parts of Linde type 4A molecular sieve (Union Carbide Corp.) having an average pore size of 20 8 Angstroms and an average particle size of 8.3 microns instead of the phosphate.

Example 42 Example 34 is repeated replacing half the phosphate with an equal amount of zeolite according to Example 40.

Example 43 30

Example 34 is repeated again, replacing the 35 parts phosphate with an equal amount of PLAC (polyhydroxyacrylic acid lactone).

35

Claims (13)

1. Transparent, water-soluble, non-sticky and substantially non-hygroscopic detergent balls, characterized in that they comprise 5 I. a matrix of (A) soap, (B) sintered and (C) solvent component, of which the soap component (A) comprises from 15 to 50% by weight of the matrix and comprises an alkali metal, alkaline earth metal, 10 ammonium or amine salt of Cg_22 "fe (its acid, which soap component of the matrix provides at most about 30% salts of fatty acids with more than 18 carbon atoms at most 70% of the soap present is Cig fatty acid and at most 50% is unsaturated fatty acid, and at most 25% of said salts are potassium salts, the soap having a weighted average carbon content of at least C₂, where the synthetic detergent component (B) constitutes from 10 to 65% by weight of the matrix and comprises at least one water-soluble member of the group comprising anionic, organic sulfonates, anionic alcohol sulfates, anionic ether sulfates, anionic ether phosphates and nonionic aliphatic detergents, but at most approx. 35%, when said synthetic detergent component (B) consists essentially entirely of anionic, organic sulfonates or anionic alcohol sulfates or mixtures thereof, and wherein the solvent component (C) constitutes from 10 to 45% by weight of the matrix and comprises a normal liquid, essential non-volatile organic solvent having a boiling point of at least 100 ° C, at least 10¾ of the component (C) being a water-soluble divalent alcohol, and which non-volatile solvent containing less than about 100 ° C. 90% of a water-insoluble solvent, and II. a water component (D) which is from 1 to 35 parts per 100 parts of the matrix I, which matrix and water component are adapted to result in substantially non-adhesive, transparent, shaping moldings which are free flowing and readily soluble in pelletted form. DK 155749B Detergent spherical balls according to claim 1, characterized in that they contain approx. 20 to 45% Component A, 20 to 55% Component B, 10 to 30% Component C, and 5 to 25 parts by weight of water per, 100 parts of matrix. 3. Detergent goblets according to claim 1, wherein they do not. contains approx. 25 to 35% component A, 30 to 45% component B, 10 to 35% component C and 10 to 15 parts by weight of water per 100 parts of matrix. Detergent spherical balls according to claim 1, characterized in that at least approx. In 40% of component A, the alkali metal salts of hydrogenated tallow fatty acids. Washing compound balls according to claim 1, characterized in that at least approx. 35% of component A are the alkali metal salts of distilled coconut oil fatty acids. Detergent spherical balls according to claim 1, characterized in that at least approx. 50% of component B is a non-ionic aliphatic detergent. 20 7 · Detergent spheres according to claim 6, characterized in that said nonionic aliphatic detergent is a reaction product of approx. 2 to 50 moles of ethylene oxide with 1 mole of a saturated aliphatic alcohol of approx. 8 to 20 carbon atoms. Detergent spherical balls according to claim 1, characterized in that at least approx. · 30% of component B is an anionic organic ether sulfate. Detergent goblets according to claim 8, characterized in that the anionic ether sulfate is an alkali metal, ammonium or amine salt of a sulfate ester of the reaction product of ca. 1 to 20 moles of ethylene oxide with 1 mole of a reactive hydrogen-containing compound having approx. 8 to 24 carbon atoms. S5 DK 155749B Detergent ball according to claim 1, characterized in that at most approx. 50% of component C are water-soluble solvents. Detergent ball according to claim 1, characterized in that approx. 10 to 90% of Component C is a water-insoluble component which is at least one member of the group comprising benzyl alcohol, lauryl alcohol or terene pine oil, and that approx. 90 to 10% is a water-soluble component which is at least one member of the group comprising water-soluble polyhydric alcohols and alkanolamines. 10 .. Detergent spherical balls according to claim 11, characterized in that approx. 10 to 50% of component C is said water-insoluble component and that approx. 90 to 50% of component C is said water-soluble component. Detergent ball according to claim 12, characterized in that at least approx. · 40% of component A is the alkali metal salts of hydrogenated tallow fatty acids, and at least approx. 35% are the alkali metal salts of distilled coconut oil fatty acids, and that at least approx. 50% of component B is the nonionic reaction product of ca. 2 to 50 moles of ethylene oxide with 1 mole of a saturated aliphatic alcohol of approx. 8 to 20 carbon atoms and that component D consists of approx. 5 to 25 parts water per 100 parts of matrix. 25 30 35