Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0026—Low foaming or foam regulating compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

• R R and R each represent hydrogen or an organic radical containing 1 to 24 carbon atoms, and R R and R are each an organic radical containing 1 to 24 carbon atoms.
• This invention relates to low-sudsing detergents. It more particularly relates to laundry detergents which contain suds inhibitors capable of effectively and lastingly inhibiting suds formation.
• alkali soaps of fatty acids particularly those having a chain length of C to C as suds inhibiting agents.
• a very effective foam inhibition can be achieved with such substances, they are not universally applicable.
• soft tap water having a hardness of 5 dH and less is used, the suds-suppressing action of the long-chain fatty acid soaps is inadequate.
• the suds reduction is limited to certain detergent combinations.
• alkyl sulfates For example, it has not been possible hitherto to reduce appreciably the sudsing action of the alkyl sulfates, and for this reason it has not been possible to use these substances (only to a slight extent if at all) in laundry and dishwater de- 3,422,020 Patented Jan. 14, 1969 tergents. Nevertheless, the use of alkyl sulfates merits special interest because of their good wash-active and physiological properties, as well as their easy biological degradability.
• Foam inhibitors of various chemical constitution have also been proposed for use together with the active detergent substances.
• no substance has become known which in low concentration brings about an effective and lasting foam suppression, independently of the chemical constitution of the surface-active substance and the content of hardness forming agents in the water, without impairing the cleaning power of the detergent.
• water-insoluble melamine derivatives of the general formula wherein R R and R each represents hydrogen or an organic radical containing 1 to 24 carbon atoms, and R R and R each represents an organic radical containing 1 to 24 carbon atoms, can be used as foam inhibitors for detergents and cleaning agents.
• the organic radicals suitably consist of straight or branched chain aliphatic, cycloaliphatic or aromatic hydrocarbons, and can contain hetero atoms such as nitrogen, oxygen or sulfur atoms, or additional substituents such as halogen atoms. They cannot, however, have any water-solubilizing groups.
• the aliphatic radicals can be alkyl or alkylene groups, for example, methyl, ethyl, propyl, bu'tyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, propylene, butylene, .decylene, octadecylene, etc.
• cycloaliphatic radicals the following may be mentioned: cyclohexyl, cyclohexenyl, alkyl-substituted cyclohexenyl, etc.
• aromatic and araliphatic hydrocarbon radicals within the scope of the invention are phenyl, naphthyl, diphenyl, alkylphenyl, in which the alkyl group contains from 1 to 20 carbon atoms.
• alkylphenyl include tolyl, Xylenyl, hexylphenyl, dodecylphenyl, etc.
• the substituents can be the same or different, that is, the substituents can be entirely or partially aliphatic, cycloa'liphatic, aromatic or araliphatic. If the groups R -R contain hetero atoms, these can be in the form of amino, nitro, ether, ester, carbonyl, and thioether groups.
• the preparation of symmetrical and asymmetrical substituted melamine derivatives is described. in Journal of American Chemical Society, vol. 73 (1951), pp. 2981 to 2986; Journal of Organic Chemistry, vol. 26 (1961), pp. 2786 to 2789.
• melamine derivatives for the sake of brevity
• melamine derivatives can be produced in the known manner, as for example by the reaction of cyanuric acid chloride with a primary or secondary amine having the above-designated number of carbon atoms or with a mixture of such amines.
• the two radicals on at least one of the amine nitrogen atoms should contain together at least 6 and preferably 8 to 20 carbon atoms.
• melamine derivatives in which R R and R each represents hydrogen; and R RyandR each represents straight-chain saturated or unsaturated hydrocarbons having a chain length of C to C and preferably C to C
• R R and R each represents hydrogen
• R RyandR each represents straight-chain saturated or unsaturated hydrocarbons having a chain length of C to C and preferably C to C
• alkylamines having-8 to 24 carbon atoms can be obtained, for example, in the prior art manner from naturally occurring fatty acid mixtures, such as coconut, palm nut and tallow fatty acids, rape-oil fatty acids and other fatty acids of vegetable or animal origin.
• the foam retardant action of the melamine derivatives is greatly dependent on temperature. Depending on the structure of the radicals R to R it does not begin to be fully effective until above a certain temperature range corresponding approximately to the fusion point of the melamine derivative.
• the foam reduction produced by the melamine derivatives which are present in the solid state is less than that produced when they are used in the liquid or semisolid state. As the temperature increases, foam inhibition is increased to the extent that the initially solid melamine derivative softens or melts, reaching its full value as soon as the fusion point is exceeded.
• the temperature range in which the melamine derivatives become effective increases with the number and chain length of the substituents.
• the total number of carbon atoms contained in the substituents R to R should not amount to more than 72, and preferably not more than 60.
• melamine derivatives in which the radicals R R and R consist of hydrogen, and the radicals R R andR have an average alkyl chain length of C to C
• the softening or melting range of these melamine derivatives generally lies between 25 and 60 C.
• a foam reduction that is substantially independent of temperature can be achieved on the one hand by the use of melamine derivatives having a 'very broad fusion range, but on the other hand also by combining two melamine derivatives one of which is of low molecular weight and melts at low temperature, while the other has long-chained substituents and melts at relatively high temperature.
• Melamine derivatives of low molecular Weight e.tg., melting at 10 to 30 0.
• the anti-foaming agents of the invention are suitable for use with many different kinds of anionic, ampholytic, cation-active and non-ionic wash-active substances.
• the anionic substances are exemplified by alkali soaps of fatty acids, and fatty -acid condensation products such as derivatives of aminocarboxylic acids; tensides of the sulfate or sulfonate type such as primary or secondary alkyl sulfates, fatty acid alkanolamide sulfates, fatty acid isothionates, fatty acid taurides, alkanesulfonates and olefin sulfonates, alkylbenzenesulfonates, alpha-sulfofatty acid esters, etc.
• the melamine derivatives are also effective in relation to ampholytes are exemplified by alkyl-betaines and alkylsulfobetaines, and in relation to cation-active tensides such as quaternary ammonium salts. Furthermore, they can be combined with non-ionic wash-active substances such as alkyl and acyl polyglycol ethers, al'kylphenol polyglycol ethers, fatty acid sugar esters, aminoxides, fatty acid alkanolamides and other fatty acid condensation products, as well as with saponines.
• non-ionic wash-active substances such as alkyl and acyl polyglycol ethers, al'kylphenol polyglycol ethers, fatty acid sugar esters, aminoxides, fatty acid alkanolamides and other fatty acid condensation products, as well as with saponines.
• the detergents and cleaning agents containing the melamine derivatives can also contain the customary fillers and additives in addition to the above-named surface-active compounds.
• These include the wash alkalis and, in particular, the orthophosphates, pyrophosphates and more highly condensed phosphates as, for example, tetrasodium and tetrapotassium pyrophosphate, pentasodiumtriphosphate, pentapotassiumtriphosphate, sodiumtetrarnetaphosphate, sodium hexametaphosphate, etc., as well as mixtures thereof; silicates, carbonates, borates and hydroxides of alkalis; oxygen-yielding or active chlorine bleaches such as sodium perborate, hydrogen peroxide, carbamic peroxide, dichlorocyanuric acid, etc.; complex formers such as polyaminopolycarboxylic acids, as for instance ethylene diaminotetraacetic acid, nitriloacetic acid, etc.;
• additives include dirt-dispersing agents, particularly cellulose derivatives such as cellulose glycolate, methyl cellulose and the like, and optical brighteners as well as perfumes and colorants. These additives have no substantial influence on the foam-suppressing action of the melamine derivatives.
• the quantities of melamine derivatives to be used in the detergent or cleansing composition depends on the quantity of the surface-active or wash-active substance present, and on the magnitude of the effect desired.
• concentrations that are important in practice range from 0.1 to no more than 20 percent of the weight of the wash-active substance. It is, of course, possible to use still greater amounts of the melamine derivative, as for example amounts of as much as 50% of the weight of wash-active substance for suppressing the sudsing action almost completely, but this is usually unnecessary with detergents.
• the special advantage of the melamine derivatives is to be seen in the fact that, even in low concentration, they produce a considerable foam suppression with all of the known wash-active substances, both in hard and in soft water, without diminishing the washing action. It is of special importance in practice that in this manner controlled suds detergents for use in machine-washing and dish'washing detergents can be manufactured on the basis of fatty alcohol sulfates. Furthermore, the additives of the invention do not impair the pulverulent qualities of deter-gents, and can easily be incorporated into the detergent concentrates prepared by spray-drying or into prepared liquid detergents.
• the melamine derivatives are particularly advantageous to mix the melamine derivatives with the solid detergents or with a component thereof. This can be done, for example, by mixing the finely divided solid, or liquid, or fused melamine derivatives, or melamine derivatives dissolved in organic solwents, as the case may be, with the powdered or granulated detergent or a part thereof, such as the sodium perborate, or by spraying them onto same.
• the melamine derivatives contained in the detergent are present in a coarsely dispersed state and are found for the most part on the surface of the detergent components. Because of their Wax-like, plastic characteristics, the melamine derivatives are substantially agglomerated and fuse with the detergent components and thus no tendency toward decomposition.
• the melamine derivatives at least envelop the detergent components.
• Particularly those preferred detergents comprise oxygen-or active chlorine-containing bleaches, in which the powdered or granulated bleach particles, preferably sodium perborate, are covered by a coating of the claimed melamine derivatives.
• the coating of the detergent particles may be accomplished by the methods well known in the art, for example, by maintaining the detergent components in a state of constant movement in the conventional mixing, granulating or coating devices and simultaneously adding thereto and/or spraying thereon the melamine derivate in finely divided or fused form. If sodium perborates are employed, a melamine derivative coating will prevent the specifically heavier perborate body from separating and/or disintegrating from the specifically lighter particles of the detergent powder during packaging, storage or transport.
• the melamine derivatives may also be used as a Waxlike coating on the detergent tablets, thus, simultaneously, protecting the tablets from untimely decomposition, as for example due to atmospheric variations.
• the sudsing action of solutions of detergent compositions in accordance with the invention was measured by the DIN method (DIN 53,902). This method makes it possible to establish the foam inhibiting action of the melamine derivatives herein taught.
• the foam volume was read 30 seconds after the beating machine had been shut off and was again read after 5 and minutes to determine the extent of the collapse of the foam. Instances in which the maximum readable foam volume of 590 ml.
• the testing apparatus is furthermore equipped with an electrical heating element, stop-cocks for filling and emptying the vessel, a thermometer, and a thermostat for keeping the temperature constant.
• the sudsin g test is carried out as follows:
• Example 1 A solution having the following composition was made to foam at 60 C. by the DIN method:
• Example 2 Example 1 was repeated, but in place of the n-dodecylbenzenesulfonate, the same quantity of fatty alcohol sulfate (chain lengthC to C average chain length C was used. The results of these tests are set out in the following table:
• n-dodecylbenzenesulfonate sodium salt
• 3% fatty alcohol polyglycol ethers alkyl chain length C to C l0 ethylene glycol groups
• penta sodium triphosphate 1% carboxymethylcellulose (sodium salt)
• Remainder sodium sulfate and water.
• Example 4 A low-sudsing machine detergent having the following composition was foamed by the DIN method at 60 C. (concentration 5 g./l.):
• n-dodecylbenzenesulfonate 7.5% soap (sodium salt) 5.0% fatty alcohol polyglycol ethers (l0 ethylene glycol groups) 1.5% carboxymethylcellulose (sodium salt) 40% penta sodium triphosphate Remainder: silicates, perborate and water.
• Example 5 (a) A solution of 5 g. of saponin per liter of water dH) was treated at 60 C. by the DIN method.
• Example 8 A boiling detergent having the following composition:
• Example 9 Example 8 was repeated, but in place of the alkylbenzenesulfonate used in that example the same amount of a sodium fatty alcohol sulfate (alkyl chain length C to C was used. In water of 15 dH, the following sudsing characteristic was found:
• Example 10 A detergent as described in Example 8 but in which the alkylbenzenesulfonate had been replaced by salts of a-sulfo fatty acid esters-that is, the detergent contained 8% of a sodium salt of an a-sulfo-fatty acid methyl ester prepared from hydrogenated palm kernel fatty acid, and
• a suds depth of to mm. is within the margin of reading error.
• Example 11 TABLE XI Percentage Depth of suds in mm.
• Example 12 If the alkylbenzenesulfonate of Example 8 was replaced with the same amount of oleylmethyltauride sodium salt, the following sudsing characteristics were found in water having a dH:
• Example 14 A fine detergent on a non-ionogenic tenside basis, having the following composition:
• Example 15 Ethoxylated nonylphenol (20 ethylene glycol groups; dehydration temperature 100 C.) in a concentration of 2 g./l. with and without the melamine derivative of Example 1 exhibited the following sudsing characteristics in the suds testing apparatus in water of 15 dH;
• Example 16 One-half of the dodecylbenzenesulfonate in the detergent composition of Example 8 was replaced with the sodium salt of a tallow fatty alcohol sulfate having a chain length of C to C
• a melamine derivative with an average carbon number of C which had been prepared in a similar manner by the reaction of cyanuric chloride with alkylamines from tallow fatty acids and had a melting range of 30 to 70 C.
• the following sudsing characteristics were observed in the suds testing apparatus in Water of 15 TABLE XVI Percentage Foam depth in min.
• Example 17 A melamine derivative was employed, which had been made by the reaction of 1 mol of cyanuric acid chloride with 3 mols of a mixture of alkylamines having a chain length of C to C (average chain length C The sudsing characteristics were determined using the above described suds tester and water of 0 and 15 dH.
• Example 18 A melamine derivative in which the radicals R to R consisted of n-butyl groups, when combined with a deter- 1 1 gent according to Example 8, had the following sudsing characteristics in water of and 15 dH (concentration used g./l.):
• Example 20 A melamine derivative produced from 1 mol of cyanuric acid chloride, 1 mol of benzylamine and 2 mols of alkylamine having a chain length of C to C (average C exhibited the following sudsing charatceristics when used in combination with a detergent according to EX- ample 9 (concentration used 5 g./ 1.; 15 dH):
• Example 21 A melamine derivative was used, in which R R and R each was represented by hydrogen, and R and R were each represented by alkyl chains having 12 to 18 15 carbon atoms, and R was a radical of the formula:
• the sudsing characteristics were determined by the DIN method at C. in water of 0 dH.
• Detergent I was a detergent according to Example 8, and detergent II a 55 detergent according to Example 9. A concentration of 5 grams per liter was used in each instance.
• the detergent had been prepared by spray drying a concentrate containing about 45% water. Thereafter, 15% sodium perborate tetrahydrate was added with mixing. The following were used as foam inhibitors:
• the items to be laundered were first given a preliminary washing at a temperature of 20 to 30 C. using a detergent concentration of 5 g./l., then the water was pumped out and the goods were washed with a new formulation at a temperature of 98 C. and a detergent concentration of 7 .5 g./l.
• Test 0 indicates a sudsing action that is largely independent of the temperature.
• Example 23 A detergent according to Example 22 and a foam inhibitor according to Example 220 were used in this experiment. In this case, however, the foam inhibitor was not mixed into the liquid detergent mixture and then spray-dried to form a concentrate, but was sprayed in the fused state onto the dry sodium perborate and toga g ML of mm after 60 gether with the latter was mixed into the washing powder. 30sec. 5min. 10 min The sudsing action was tested as described in Example max 560 400 22 in a drum washing machine containing dirty laundry. 130 80 40 The results are summarized in the following table. The 3 2% 28 results of Example 220 have been included for com 110 100 80 65 parrson:
• composition of the detergents in which the foam inhibitors of the invention preferentially find use can vary within wide limits.
• solid or powdered, lowsudsing detergents suitably contain the following as principal components:
• melamine derivative 90% inorganic wash-active salts such as for example anhydrous phosphates, alkali silicates and alkali carbonates;
• dispersing agents of high molecular weight such as carboxymethylcellulose
• Liquid detergents suitably contain:
• anhydrous phosphates preferably as potassium salts
• solubilizers preferably alkylbenzenesulfonates having lower alkyl groups
• the action of the melamine derivatives is not limited to the detergent compositions and quantity ratios stated above and in the examples.
• a low sudsing detergent consisting essentially of at least one wash-active agent selected from the group consisting of anionic, ampholytic, cation-active and non-ionic wash-active substances and 0.1 to referred to the weight of the wash active agent of a water-insoluble melamine derivative of the formula:
• R R and R each represents a member selected from the group consisting of hydrogen and organic radicals containing 1 to 24 carbon atoms, and R R and R each represents an organic radical containing 1 to 24 carbon atoms wherein at least one of the groups of R plus R R plus R and R plus R contains a total of at least 6 carbon atoms and wherein the total number of carbon atoms contained in said groups R R does not exceed 72, said organic radicals R R being free of any water-solubilizing groups.
• R R and R each represents hydrogen am R R and R each represents a hydrocarbon group containing 8 to 20 carbon atoms.
• a low sudsing detergent according to claim 1 consisting essentially of 5-60% wash-active agent selected from the group consisting of anionic, ampholytic, cation-active and nonionic wash-active substances,
• R R and R each represents a member selected from the group consisting of hydrogen and organic radicals containing 1 to 24 carbon atoms, and R R and R each represents an organic radical containing 1 to 24 carbon atoms,
• a low sudsing detergent according to claim 1 consisting essentially of water and 550% wash-active agent selected from the group consisting of anionic, ampholytic, cation-active and nonionic wash-active substances,
• R R and R each represents a member selected from the group consisting of hydrogen and organic radicals containing 1 to 24 carbon atoms, and R R and R each represents an organic radical containing 1 to 24 carbon atoms,
• a low sudsing detergent according to claim 1 consisting essentially of 15 16 12-14% n-dodecylbenzem: sulfonate (sodium salt) 5 References Cited 3;Z;up:;Cyl alcohol polyglycolether (10 ethylene UNITED STATES PATENTS 40 45% pentasodium triphosphate 3,318,817 5/ 1967 Cunningham 252-437 5 Sodium Silicate (Na2)'3 3 sioz) 5 3,336,231 8/1967 Marsh et al 202 102 3% magnesium silicate O N PATENTS 0.5-1.5 carboxymethyl cellulose (sodium salt) 1,124,956 8/1959 Germany.

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• 1965
  • 1965-02-11 DE DEH55120A patent/DE1257338B/de active Pending
  • 1965-12-15 DE DE19651467620 patent/DE1467620A1/de not_active Withdrawn
• 1966
  • 1966-02-07 US US525765A patent/US3422020A/en not_active Expired - Lifetime
  • 1966-02-09 BE BE676235D patent/BE676235A/xx unknown
  • 1966-02-10 GB GB5801/66A patent/GB1107194A/en not_active Expired
  • 1966-02-10 DK DK70066AA patent/DK126600B/da unknown
  • 1966-02-10 CH CH187366A patent/CH488009A/de not_active IP Right Cessation
  • 1966-02-11 FR FR49273A patent/FR1469343A/fr not_active Expired
  • 1966-02-11 SE SE01804/66A patent/SE337646B/xx unknown
  • 1966-02-11 NL NL666601784A patent/NL140897B/nl unknown
  • 1966-06-25 DE DE1617116A patent/DE1617116C3/de not_active Expired

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