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
  • C11D10/00—Compositions of detergents, not provided for by one single preceding group
  • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
  • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
• • 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
  • C11D3/001—Softening 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• customary surface-active compounds utilizable in neutral to alkaline textile washing baths selected from the group consisting of anionic surface-active compounds, amphoten'c surfaceactive compounds, non-ionic surface-active compounds, and mixtures thereof, wherein not more than 50% by weight of said surface-active compounds are non-ionic surface-active compounds, and
• An object of the invention is the obtention of washing compositions for textiles, especially fine-wash articles and easy-care textiles containing textile softeners which are substantive and compatible with neutral to alkaline textile washing agents.
• Another object of the invention is the obtention of detergent compositions containing textile softeners consisting essentially of:
• the invention is based on the discovery that the handle of the laundered fabrics is improved, if in the detergents or auxiliary used for the laundry in addition to anionic, non-ionic and/or amphoteric surface-active agents, and possibly traditional components of such agents, also reaction products of higher fatty acids with hydroxyalkyl polyamines as textile softeners are present.
• the detergent compositions of the present invention containing the aforementioned textile softeners comprise:
• the fatty acid monoamides used as textile softeners are preferably derived from the hydroxyalkyl derivatives of ethylenediamine or diethylenetriamine, such as, for example, hydroxyethylethylenediamine, dihydroxyethylethylenediamine, hydroxyethyldiethylenetriamine, hydroxypropyldiethylenetriamine, etc., that is, from hydroxyalkyl polyamines.
• Hydroxyalkylpolyamines are understood to mean compounds possessing at least one hydroxyethyl, hydroxypropyl or dihydroxypropyl group and at least two hydrogen atoms bonded to nitrogen.
• the derivatives of N-hydroxyethylethylenediamine are of special practical importance.
• Such fatty-acid monoamides are obtained by the reaction of 0.5 to 1.1, preferably 0.9 to 1.0 mols of a fatty acid radical in the form of the fatty acid itself or of a fatty acid ester, especially of a lower alkyl ester, with one mol of the hydroxyalkylpolyamine.
• fatty acid triglycerides which in practice correspond to 3 mols of fatty acid residues, can be used as fatty acid esters.
• the products may also contain fatty acid residues having 8 to 14 carbon atoms.
• the textile-softening properties of the fatty acid monoamides present in the products according to the invention are not thereby impaired. It is preferable, how- .ever, as already mentioned, to use fatty acid compounds such that the fatty acid residues of the monoamides consist of at least 50%, preferably at least 80% of those having 16 to 24 carbon atoms.
• fatty acid glycerides especially fatty acid triglycerides
• fatty acid partial glycerides may be present in the fatty acid monoamide as associated substances in amounts less than 5% by weight, preferably less than 2.5% of weight of the textile softener.
• the reaction is carried out simply by heating a melt of hydroxyalkylpolyamine and fatty acid, or fatty acid alkyl ester, or fatty acid glyceride, or a solution of the components in inert, non-polar solvents such as petroleum hydrocarbons, toluene, xylene, etc. of temperatures from to 180 C., preferably to C.
• the reaction time is up to 25 hours, depending on the temperature and the fatty acid component used. If fatty acids or their lower alkyl esters are the starting materials, a practically complete reaction can then be obtained when from 90% to 95% of the calculated amount of water or alcohol formed has distilled off.
• fatty acid partial glycerides are practically not contained in the reaction product, or at most in fractions of less than 5% by weight, preferably less than 2.5 by weight.
• the condensation product used according to the invention therefore preferably contains no fatty acid partial glycerides as impurities.
• the fatty acid monoamides of hydroxyalkylpolyamines used as textile softeners according to the invention represent the chief product which is obtained in the condensation of fatty acids or fatty acid alkyl esters or fatty acid triglycerides with hydroxyalkylpolyamines in the said molar ratios. If the starting substance in the preparation is, for example, N-hydroxyethylethylenediamine, the N- monoacyl-hydroxy-ethyl-ethylenediamine is obtained as the main product, of which at least 50%, preferably at least 65% is contained in the technical condensation product, and which is regarded as the active agent causing the textile-softening action.
• the impurities may include fatty acid diamides, fatty acid monoamide esters or diamide esters as byproducts of the condensation. These impurities do not impair the textile-softening action of the fatty acid monoamides, so that the resulting products may be used withoutfurther purification, possibly after removing the solvent, as textile softeners in combination with washing compositions.
• the technical products used according to the invention are solid or highly viscous liquid substances at normal temperature.
• the fatty acid monoamides from hydroxyethylethylenediamine and mostly saturated fatty acid residues represent preferred forms of the textile softeners used according to the invention.
• the degree of saturation of the fatty acid residues is unimportant, but in the compositions according to the invention with preponderantly saturated fatty acid residues (with iodine values below 30, preferably below 10) are preferred on account of their better stability on storage.
• the fatty acid derivatives used for the preparation of the fatty acid monoamides may be derived, for example, from palmitic, stearic, oleic, arachidic or behenic acids. If fatty acid glycerides, or fats of natural origin are used, those with preferably 16 to 24 carbon atoms in the fatty acid residues are suitable. Provided the glycerides also contain fatty acid residues with 8 to 14 carbon atoms, the fraction of fatty acid residues with 16 to 24 carbon atoms, in the mixed glycerides or glyceride mixtures should amount to at least 50%, preferably at least 80%.
• Suitable fats of natural origin are the fats of plants, land or sea animals, for example palm, olive, linseed, cottonseed, soya, groundnut and rape oils, lard, tallow, and especially the wholly or partially hardened products of these fats, and also hardened fish or whale oils.
• the incorporation of the fatty acid monoamides for the preparation of, in practice, specially interesting washing compositions with a textile-softening action may be effected by various known methods.
• the fatty acid monoamide it is advisable for the fatty acid monoamide to be present in very fine dispersion in the washing composition according to the invention.
• This very fine dispersion may be obtained either by uniformly mixing finely powdered fatty acid monoamide with the other particles of washing composition, or by spraying the fatty acid monoamide in melted form or dissolved or dispersed in a suitable liquid carrier on the other solid particles of washing powder, so that the latter are wholly or partly coated, or by incorporating the fatty acid monoamide in the paste of washing composition to be atomized, for which aqueous dispersions of the fatty acid monoamide are specially suitable.
• a surface-active component consisting substantially of anionic surface-active compounds of the sulfonate and/or sulfate type with preferably 8 to 18 carbon atoms in the hydrophobic residue, soaps and possibly non-ionic surface-active compounds, where the non-ionic surface-active compounds which may be present constitute not more than 50% by weight and preferably not more than 35% by weight of this surface-active component.
• washing composition constituents especially alkaline to neutral reacting builders, complexing agents, bleaches, dirt carriers, enzymes, brighteners, perfume, dyestuff, water, etc.
• washing composition components being chosen within the above-indicated range, so that the fatty acid monoamides serving as textile softeners constitute 5% to 20%, preferably 7.5% to 15%, by weight of the total washing composition.
• the relative proportion of the anionic surface-active compounds of the sulfonate and/or sulfate type to the soap in the washing compositions lies in the range of :1 to 1:5, preferably 7:1 to 1:2.
• washing compositions of the present invention which are to be used as fine washing compositions generally have the following formulation:
• washing composition constituents as for example, dirt carriers, enzymes, brighteners, perfume, dyestuif, water, etc.
• the amounts of the washing composition components being chosen within the above-indicated range so that the fatty acid monoamides serving as textile softeners constitute from 5% to 20%, preferably 7.5% to by weight of the total washing composition.
• the washing compositions may also contain a bleaching component which, in the above formulation, is re- 7 stituents. If a bleaching component is present, this is preferably perborate, possibly in combination with activators, or active chlorine compounds.
• a bleaching component is present, this is preferably perborate, possibly in combination with activators, or active chlorine compounds.
• the textile softeners used according to the invention are preferably incorporated in fine washing compositions suitable for machine washing, which need not contain bleaching components.
• the washing compositions according to the invention are preferably suitable for washing of fine laundry articles and easy-care textiles especially those of cotton, polyester, polyacrylonitrile and polyamide, especially in the form of woven or knitted fabrics. It is preferred that the laundering be effected at a temperature in the range of 30 to 60 C. It is also possible though to launder at temperatures up to boiling temperature.
• the anionic, amphoteric or non-ionic surface-active compounds contain in the molecule at least one hydrophobic residue mostly containing 8 to 26, preferably 10 to 22 and especially 10 to 18 carbon atoms, and at least one anionic, non-ionic or amphoteric water-solubilizing group.
• the preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing group or through intermediate members.
• Suitable inter mediate members are, for example, benzene rings, carboxylic acid ester or carbon amide groups, residues of polyhydric alcohols linked in etheror ester-like form, such as for example, those of ethylene glycol, propylene glycol, glycerine or corresponding polyether residues.
• the hydrophobic residue is preferably an aliphatic hydrocarbon. residue having 10 to 18, preferably 12 to 18 carbon atoms, but deviations from this preferred range of numbers are possible, depending on the nature of the surface-active compound in question.
• Soaps which are derived from natural or synthetic fatty acids, possibly from resin or naphthenic acids, are utilizable as the anionic detergent substances, especially when these acids have iodine values of not more than 30 and preferably less than 10.
• the sulfonates and sulfates possess particular practical importance.
• the sulfonates includes, for example, the alkylarylsulfonates, especially the alkylbenzene-sulfouates, which among others, are obtained from preferably straight chain, aliphatic hydrocarbons having 9 to 15, preferably 10 to 14, carbon atoms, by chlorination and condensation with benzene or from corresponding olefins with terminal or non-terminal double bonds by condensation with benzene, and sulfonation of the alkylbenzenes obtained.
• the alkylarylsulfonates especially the alkylbenzene-sulfouates, which among others, are obtained from preferably straight chain, aliphatic hydrocarbons having 9 to 15, preferably 10 to 14, carbon atoms, by chlorination and condensation with benzene or from corresponding olefins with terminal or non-terminal double bonds by condensation with benzene, and sulfonation of the alkylbenzenes obtained.
• aliphatic sulfonates are of interest such as are obtainable, for example, from preferably saturated hydrocarbons containing 8 to 18 and preferably 10 to 16, carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and conversion of the products thereby obtained into the sulfonates.
• alkene sulfonates, hydroxyalkane sulfonates and alkane di-sulfonates are also useful as aliphatic sulfonates, such as are obtained, for example, from C to C preferably C to C olefins with terminal or non-terminal double bonds by sulfonation with sulfur dioxide, and acid or alkaline hydrolysis of the sulfonation products.
• the sulfonate group is frequently attached to a secondary carbon atom.
• sulfonates with a primary, for example, terminal, sulfonate group can also be prepared by reacting terminal olefins with a bisulfite.
• the sulfonates to be used according to the invention also include salts, preferably dialkali metal salts of a-sulfofatty acids as well as esters of a-sulfo-fatty acids with monoor poly-hydric alcohols containing 1 to 4 and preferably 1 to 2 carbon atoms.
• sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor di-carboxylic acids containing 1 to 8 carbon atoms, alkylglycerylether sul fonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.
• Surface-active compounds of the sulfate type include fatty alcohol sulfates, especially those derived from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Sulfonation products of the sulfate type utilizable according to the invention can also be prepared from C to C olefins with terminal or non-terminal double bonds. In addition, belonging to this group of surfaceactive compounds are sulfated fatty acid alkyloamides,
• sulfated monoglycerides and sulfated products of ethoxylated and/or propoxylated compounds such as fatty alcohols, alkylphenols with 8 to 15 carbon atoms in the alkyl residue, fatty acid amides, fatty acid alkylolamides and so forth, where 0.5 to 20, preferably 1 to 8, and advantageously 2 to 4 mol of ethylene and/or propylene oxide are added to one mol of said compounds to be ethoxylated and/or propoxylated.
• the washing agents according to the invention may also contain surface-active synthetic carboxylates, for example, the fatty acid esters or fatty alcohol ethers of hydroxy-carboxylic acids as well as the fatty acid amide condensation products of fatty acids or sulfonic acids with amino-carboxylic acids, for example, glycocoll, sarcosine or protein hydrolysates.
• surface-active synthetic carboxylates for example, the fatty acid esters or fatty alcohol ethers of hydroxy-carboxylic acids as well as the fatty acid amide condensation products of fatty acids or sulfonic acids with amino-carboxylic acids, for example, glycocoll, sarcosine or protein hydrolysates.
• Non-ionics products which owe their solubility in water to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups, and very generally to a number of hydroxyl groups, belong to the non-ionic surface-active compounds, denoted here as Non-ionics for the sake of simplicity.
• Non-ionics may contain, per molecule, 4 to 100, preferably 6 to 40 and especially 8 to 20, ether residues above all ethylene glycol ether residues.
• propylene or butylene glycol ether residues may be present either in these polyglycol ether residues or at their ends.
• Non-ionics products known by the trade names of Pluronics and "Tetronics belong to the Non-ionics.” They are obtained from water-insoluble polypropylene 3 glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to 8, preferably 3 to 6 carbon atoms and/or from water-insoluble propoxylated alkylenediamines. These water-insoluble (for example, hydrophobic) propylene oxide derivatives are converted into the-said “Non-ionics” by ethoxylation until they become soluble in water. Finally, the reactionproducts of the above-mentioned aliphatic alcohols with propylene oxide known as Ucon-Fluid,” some of which are still water-soluble, are useful as Non-ionics.
• Ucon-Fluid reactionproducts of the above-mentioned aliphatic alcohols with propylene oxide
• Non-ionics are fatty acid or sulfonic acid alkylolamides, which are derived, for example, from monoor di-ethanolamines, dihydroxypropylamine or ,other polyhydroxylalkylamines, for example, the glycamines. They can be replaced by amides of higher primary or secondary alkylamines and polyhydroxycarboxylic acids.
• Non-ionics derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyl and/or alkylol residues containing up to 4 carbon atoms each are of particular interest.
• Amphoteric surface-active compounds contain in the molecule both acid and basic hydrophilic groups.
• To the acid groups belong carboxylic acid, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups.
• the basic groups may be primary, secondary, tertiary and quaternary ammonium groups.
• Amphoteric compounds with quaternary ammonium groups are of the betaine type.
• carboxy, sulfate and sulfonate betaines have special practical interest.
• Suitable sulfobetaines are obtained, for example, by reacting tertiary amines containing at least one hydrophobic alkyl residue with sultones, for example propaneor butane-sultone.
• Corresponding carboxybetaines are obtained by reacting the said tertiary amines with chloroacetic acid, its salts or with chloroacetic acid esters and fission of the ester linkage.
• the foaming capacity of the washing agents according to the invention may be increased or reduced by suitable combinations of different surface-active compounds as well as non-surface-active compounds.
• Suitable foam stabilizers in the case of surface-active compounds of the sulfonate or sulfate type are chiefly surface-active carboxyor sulfo-betaines and also the above-mentioned non-ionics of the alkylolamide type. Moreover, fatty alcohols or higher terminal diols are utilizable for this purpose.
• Products with a reduced foaming capacity are chiefly intended for use in washing and dish-washing machines, in which in some cases a limited inhibition of foam is sufiicient, while in other cases a stronger anti-foaming effect may be desired. Products which still foam in the average range of temperature up to about 65 C., but develop less and less foam as higher temperature (70- C.) are reached, are of particular practical importance.
• a reduced foaming power is often obtained with combinations of different types of surface-active compound, especially with combinations of synthetic anionic surfaceactive compounds, above all of (1) sulfates and/0r sulfonates or of (2) non-ionics on the one hand and (3) soaps on the other hand.
• the foaming behavior can be influenced by the respective soap used.
• soaps from preferably saturated fatty acids with 12 to 18 carbon atoms the inhibition of foam is small, while a stronger anti-foaming effect is attained, especially in the higher temperature range, by soaps from saturated fatty acid mixtures with 20 to 26, preferably 20 to 22 carbon atoms, the amount of which may constitute 5 to 10% by weight of the total soap fraction present in the surface-active combination.
• the foaming capacity of the surface-active compounds can also be reduced by additions of known, nonsurface-active foam inhibitors.
• these include possibly chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mole of cyanuric acid chloride with 2 to 3 mol of a monoand/or di-alkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl residue.
• Aminotriazineor melamine-derivatives which contain polypropylene glycol or polybutylene glycol chains, while 10 to 100 of such glycol residues may be contained in the molecule, have a similar action.
• Such compounds are obtained, for example, by addition of corresponding amounts of propylene and/or butylene oxide to aminotriazines, especially to melamine.
• Products preferably used are obtained, for example, by reacting 1 mol of melamine with at least 20 mol of propylene oxide or at least 10 mol of butylene oxide.
• Products have been found to be specially active which are obtained by addition of 5 to 10 mol of propylene oxide to 1 mol of melamine and further addition of 10 to 50 mol of butylene oxide to this propylene oxide derivative.
• the trito hexa-alkylmelamines or dito tetra-alkyldiaminochlorotriazines so obtained have a remarkably broad active spectrum independent of the nature of the surface-active compound in question.
• non-surface-active, water-insoluble, organic compounds such as paraflins or haloparatfins with melting points below 100 C.
• aliphatic C to C -ketones and aliphatic carboxylic acid esters which contain at least 18 carbon atoms in the acid or in the alcohol residue, possibly also in both of these two residues (for example triglycerides or fatty acid-fatty alcohol esters), can also be used as foam inhibitors, especially in combination with anionic synthetic surface-active compounds and soaps.
• non-surface-active foam inhibitors are often only fully active at temperatures at which they are present in the liquid state, so that the foaming behavior of the products can be controlled by choice of suitable foam inhibitors in a similar way to the choice of soaps from fatty acids of suitable chain lengths.
• Particularly weakly foaming non-ionics which may be used both alone and in combination with anionic, amphoteric and non-ionic surface-active compounds and reduce the foaming power of more strongly foaming, especially non-ionic, surface-active compounds, are addition products of propylene oxide to the above-described surface-active polyethylene glycol ethers, and also the abovedescribed Pluronics, Tetronics and Ucn" fluid.
• the complete washing compositions contain builders and inorganic salts as well as inorganic and organic complex-forming compounds.
• Salts which are weakly acid, neutral or alkaline reacting are utilizable in the compositions of the invention, for example, the alkali metal bicarbonates, carbonates, silicates, orthophosphates, sulfates, dior tetra-alkali metal pyrophosphates, complex forming alkali metal metaphosphates and the alkali metal salts of organic, non-surfaceactive sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms.
• water-soluble salts of higher molecular weight polycarboxylic acids are useful as builders, especially polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid.
• Mixed polymerizates of these acids with one another or with other polymerizable substances as for example with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-3-butane-carboxylic acid and also with vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are also useful.
• Suitable complex forming builders are the weakly acid reacting metaphosphates and the alkaline reacting polyphosphates, especially the pyro-, tripolyor tetrapolyphosphates. They may be replaced by known organic complex-forming compounds or be combined with them.
• the latter include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, polyalkylene-polyamine-N-polyacetic acids and other known organic complex-forming compounds. Combinations of different complex-forming compounds may also be used. Diand poly-phosphoinc acids of the following constitutions also belong to the other known complex-forming compounds.
• R represents alkyl and R represents alkylene radicals with 1 to 8, preferably 1 to 4, carbon atoms
• X and Y represent hydrogen atoms or alkyl radicals with 1 to 4 carbon atoms.
• Carboxy-methylenephosphonic acid HOOC-CH PO(OH) is also useful as a complexforming compound according to the invention. All these complex-forming compounds may be present as the free acids, but are preferably present as the alkali metal salts.
• the bleaching agents based on active oxygen are, especially, the inorganic percompounds, for example, perpyrophosphates, perpolyphosphates, percarbonates and perborates.
• the commercial sodium perborate of the approximate composition NaBO -H O -3H O is of particular practical importance. Partly or completely dehydrated perborates, that is up to the approximate composition NaBo -H o may also be used in its place.
• active oxygen containing borates, NaBO -H O are also useful in which the ratio Na O:B O is less than 0.5:1 and preferably lies in the region of 0.4 to 0.15: 1, and in which the ratio H O :Na lies in the region of 0.5 to 4:1.
• the perborates may be wholly or partly replaced by other inorganic per-compounds, especially peroxyhydrates, such as for example, the peroxyhydrates of ortho-, pyro or poly-phosphates, for example of tripolyphosphates, and also of the carbonates.
• the active chlorine compounds useful as bleaching agents may be inorganic or organic.
• the inorganic active chlorine compounds include alkali metal hypochlorites, which may be used especially in the form of their mixed salts or addition compounds with orthophosphates or condensed phosphates, as for example, with pyroand poly-phosphates, or with alkali metal silicates. If the washing agents and washing agent adjuvants contain monopersulfates and chlorides, active chlorine is formed m aqueous solution.
• Suitable organic active chlorine compounds are, in particular, the N-chloro-compounds in which one or two chlorine atoms are linked to a nitrogen atom, the third valency of the nitrogen atom being preferably linked to a negative group, especially a CO- or S0 group.
• These compounds include dichloroand trichloro-cyanuric acid, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoin and chlorinated melamine.
• the washing agents may also contain stabilizers for the bleaching component, especially for the percompounds.
• stabilizers for the bleaching component especially for the percompounds.
• the above-indicated complex-forming compounds often have a stabilizing action.
• different kinds of stabilizers may be present, for example, those which act through their large surface area.
• These customary water-soluble or waterinsoluble stabilizers are utilized in amounts up to 10%, preferably from 0.25% to 8% by weight.
• Suitable water-soluble stabilizers which may be present together with water-insoluble stabilizers, are the above referred-to organic complex-forming compounds, the amount of which may constitute 0.25% to preferably 0.5% to 2.5% of the weight of the total preparation, depending on the strength of the complex formed.
• the action of the bleaching components and above all of the percompounds can be increased by known activators, such as small quantities of heavy metal ions, especially copper ions, which may preferably be present as mixed silicates of magnesium.
• dire carriers or soil suspension agents may be contained in the washing agents according to the invention, which keep the dirt, detached from the fiber, suspended in the washing bath and thus prevent graying.
• water-soluble colloids of mostly organic nature are suitable, as for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ethercarboxylic acids or ethersulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acid groups are also suitable for this purpose.
• soluble starch and starch products other than those named above can be used, as for example, degraded starch. aldehyde starches and so on. Polyvinylpyrrolidone is also utilizable.
• the components of the washing compositions according to the invention are usually selected so that the preparations have a neutral to distinctly alkaline reaction, so that the pH value of a 1% solution of the preparation usually lies in the region of 7 to 12.
• the brighteners which may be used are mostly, if not ,exclusively, derivatives of diaminostilbenesulfonic acid,
• brighteners from the class of diaminostilbenesulfonic acid derivatives are compounds according to the formula SO!- R:
• R and R signify halogen atoms or alkoxy groups, amino groups or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines, or residues of aminosulfonic acids, while aliphatic residues present in the above groups preferably contain 1 to 4 and especially 2 to 4 carbon atoms, and in the heterocyclic ring systems, fiveor six-membered rings are usually concerned.
• Aniline, anthranilic acid or anilinesulfonic acid residues are preferred as the aromatic amines.
• Brighteners derived from diaminostilbenesulfonic acid are mostly used as cotton brighteners.
• the following products derived from the above formula in which R represents the residue NHC H and R may represent the following present on the market: NH,
• Diarylpyrazolines of Formulas II and III belong to the polyamide brighteners, of which again a few have a certain afi'inity for cotton fibers:
• R and R represent hydrogen atoms, or alkyl or aryl residues possibly substituted by carboxyl, carbonamide or ester groups.
• R and R represent hydrogen or short-chain alkyl resiues.
• Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms.
• 9-cyano-anthracene is also on the market as a polyamide brightener.
• polyamide brighteners for example 4-methyl-7-dimethylaminoor 4-methyl-7-diethylamino-coumarin.
• polyamide brighteners are the compounds 1-(benzimidazolyl-2)-2-(N-hydroxyethyl benzimidazo1yl-2')-ethylene and l-N-ethyl-3-phenyl-7-diethylamino-carbostyril.
• Suitable brighteners for polyester and polyamide fibers are the compounds 2,5-di-(benzoxazolyl-2')-thiophene and 1,2-di-(5'-methyl-benzoxazolyl- 2)-ethylene.
• the brighteners are present together with other constituents of the products according to the invention as 0 aqueous solutions or pastes and are converted into the solid state by spray drying, it is advisable to incorporate at least 0.1% and preferably 0.2 to 1% by weight of the solid products, of organic complex-forming compounds for the stabilization of the brighteners.
• the enzymes which may be utilized may be obtained from animals, microorganisms such as bacteria or fungi and plants, especially from digestive ferrnents, yeasts and strains of bacteria. They usually represent a complicated mixture composed of various enzymatic active substances. According to their action they are denoted as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases 0r nucleases.
• the enzymatic substances, particularly proteases or amylases, obtained from strains of bacteria or fungi, such as Bascillus subrilis and Strepromyces griseus, are of special interest.
• enzymes are pepsin, pancreatin, trypsin, papain and diastase.
• the enzyme preparations obtained from Bacillus subn'lis have the advantage, as compared with the last-named enzymes, in that they are relatively stable with respect to alkali, percompounds and anionic detergents, and even at temperatures between 45 and C. are still not appreciable inactivated.
• the enzymes are marketed by the producers usually in the form of aqueous solutions of active substances or with addition of blending agents, as powders. Suitable blending agents are sodium sulfate, sodium chloride, alkali metal ortho-, pyroor poly-phosphates, especially tripolyphosphates.
• Suitable blending agents are sodium sulfate, sodium chloride, alkali metal ortho-, pyroor poly-phosphates, especially tripolyphosphates.
• the still moist enzyme preparations are frequently incorporated with calcined salts, which then, in
• liquid or paste-like or possibly solid non-ionic, preferably surface-active, organic compounds, especially the above-described Non-ionics can also be used at room temperature of binding the enzymatic active substance to the respective preparation to be made.
• a mixture of the components of the combination of surface-active compounds or of the washing agent and the enzymatic substance, for example, is sprayed with these non-ionic products, or the enzymatic substance is dispersed in the said non-ionic substances and this dispersion is united with the other constituents of the product.
• the other constituents of the products are solids, the dispersion of the enzymatic substances in the non-ionic component can be sprayed on the other solid constituents.
• the enzymes, or combinations of enzymes with variable action are generally used in quantities such that the finished products have protease activities of 50 to 5000, preferably 100 to 2500 LVE/ g. and/or amylase activities of 20 to 5000, preferably 50 to 2000 SKBE/g. and/or lipase activities of 2 to 1000, preferably 5 to 500 IE/ g.
• the above data on the content of enzymes and activities of the preparations according to the invention are obtained from the activities of those enzyme preparations which are available at the present time, from the standpoint of economy, for use in the washing agent field. From the technical-chemical standpoint the enzyme activities of the preparations according to the invention can be increased, if feasible, so that the activties as regards proteases and amylases can be raised to 5 times, and as regards lipases, to times the above given maximum values. Therefore, should, in the future, enzyme preparations with higher enzyme contents be supplied, which also appear suitable economically for use in washing agents, one has the choice either of keeping the enzyme activity of the preparation to the above given height by use of smaller amounts of enzymes or of increasing the enzyme activity with use of the same amount of enzymes.
• compositions of a few preparations according to the invention describe compositions of a few preparations according to the invention.
• the salt-like components contained therein, salt-like surface-active compounds, other organic salts and inorganic salts, are present as sodium salts, provided it is not expressly given otherwise, although other alkali metal and ammonium salts may be utilized.
• the notations and abbreviations used signify:
• ABS is the salt of an alkylbenzenesulfonic acid with 10 to 15, preferably 11 to 13, carbon atoms in the alkyl chain, obtained by condensing straight chain olefins with benzene and sulfonating the alkylbenzene so obtained.
• Olefinsulfonate is a sulfonate obtained from straight chain olefins (12 to 16 carbon atoms) with terminal or non-terminal double bonds by sulfonation with S0 and hydrolysis of the sulfonation product with an alkali liquor.
• the said sulfonate consists substantially of alkene sulfonate and hydroxyalkane sulfonate, but also contains small quantities of alkane disulfonates.
• Each olefinsulfonate-containing preparation was prepared using two different types of olefinsulfonate; one was from a mixture of straight-chain terminal olefins, and the other was prepared from a mixture of non-terminal olefins.
• Alkane sulfonate is a sulfonate obtained from paraffins with 12 to 16 carbon atoms by the sulfoxidation method.
• Fatty acid ester sulfonate is a sulfonate obtained from the methyl ester of a hardened tallow fatty acid by sulfonating with S0 Oleyl alcohol ether sulfate (OA-EO-sulfate) or Tallow alcohol ether sulfate (TA-EO-sulfate) or coconut alcohol ether sulfate (CA-EO-sulfate) are the sulfated products of addition of 2 mols of ethylene oxide (E0) to 1 mol of oleyl alcohol or of 3 mols of ethylene oxide to 1 mol of tallow fatty alcohol or of 2 mols of ethylene oxide to 1 mol of coconut fatty alcohol.
• Tallow alcohol sulfate TA-sulfate
• CA-sulfate coconut alcohol sulfate
• Oleyl alcohol+5 E0 (OA-l-SEO) or Oleyl alcohol +10EO (OA-l-IOEO) are the products of addition of five or ten mols of ethylene oxide to one mol of a commercial oleyl alcohol.
• Coconut alcohol+20EO (CA+20EO) is the product of addition of 20 mols of ethylene oxide to 1 mol of a fatty alcohol prepared from coconut fatty acid.
• Coconut alc0hol+9EO+l2PO (CA+9EO+12PO) is the product of addition of 9 mols of ethylene oxide to 1 mol of a fatty alcohol prepared from coconut fatty acid, reacted with 12 mols of propylene oxide.
• Tallow alcohol-H4130 (TA+14EO) is the product of addition of 14 mols of ethylene oxide to 1 mol of a fatty alcohol prepared from tallow fatty acid.
• Nonylphenol+9.5 EO is the product of addition of 9.5 mols of ethylene oxide to 1 mol of nonylphenol.
• FA-amide-l-SE is the product of addition of 8 mols of ethylene oxide to 1 mol of a hardened tallow fatty acid amide.
• HEDP is the salt of hydroxyethane-diphosphonic acid.
• EDTA is the salt of ethylenediaminetetraacetic acid.
• NTA is the salt of nitrilotriacetic acid.
• Perborate is a product of the approximate composition NaBO .H O .3H O containing about 10% of active oxygen.
• CMC is the salt of carboxymethyl cellulose.
• compositions of the fatty acid mixtures from which the various soaps contained in the combinations of surface-active compounds or washing agent were produced may be taken from the following Table I:
• a foam inhibitor a mixture of approximately 45% of a di-(alkylamino)-monochlrotriazine and approximately 55% of an N-N'-N"-trialkyl melamine was used.
• the alkyl residues were present as a mixture of homologs with 8 to 18 carbon atoms.
• the monochloro triazine derivative or trialkylmelamine could also be used with similar success.
• the products described contained synthetic sulfates or sulfonates together with a soap, the other nonsurfactant foam inhibitors mentioned in the description such as, for example, paraffin oil or paraffin could be used.
• the foam inhibitor used dissolved in a suitable organic solvent or in melted condition, was sprayed through a nozzle onto the moving powdered preparation.
• the amounts indicated for the surfactants relate to pure active substances.
• small quantities of byproducts originating from the manufacture are also present.
• Na SO means that small quantities of sodium sulfate as impurity are present, introduced by the anionic surfactants used.
• the remainder consists substantially of water, also dyes, and perfumes. Where the Na SO quantity is given as the remainder also comprises the existing sodiuum sulfate.
• the product had the following characteristics: acid value 0.9; hydroxyl number (OH value) 340; titratable nitrogen N 6.1%.
• the fatty acid monoamides can also be prepared by reacting fatty acid triglycerides with N-hydroxyethylethylenediamine (in the corresponding molar ratio of 0.9 mol fatty acid residues: 1 mol amine). In these products a content of fatty acid partial glycerides is not detectable by chromatography and therefore is certainly less than 1%, since a content of 1% would still be clearly detectable.
• textile softeners used according to the invention are also the reaction products from wholly or partly hydrogenated fats, such as tallow, cottonseed oil, palm oil, etc. which consist substantially of fatty acid residues containing 16 to 18 carbon atoms, or the corresponding free fatty acids or their lower alkyl esters, with N-hydroxyethylethylenediamine (molar ratio fatty acid residues: amine is 0.9: 1.0).
• wholly or partly hydrogenated fats such as tallow, cottonseed oil, palm oil, etc. which consist substantially of fatty acid residues containing 16 to 18 carbon atoms, or the corresponding free fatty acids or their lower alkyl esters, with N-hydroxyethylethylenediamine (molar ratio fatty acid residues: amine is 0.9: 1.0).
• Component of surfactant AB S Olefinsulfonate FA-ester sulfonate CA sulfate 8 8 TA sulfate- 3 OA+10EO 16 16 16 16 CA+20EO 'CA+9EO+12PO Soap 1218 Soap 1222 14 Fabric softener 27 33 34 34 Foam inhibitor 5 2 2 3 4 3 Percent by weight component in the surfactant combination according to- Ex. Ex. Ex. Ex. Ex. Ex. Ex. combination T14 T15 T16 T17 T18 T19 T20 AB S 34 Alkane sulfonate Olefinsulfonate FA-ester sulfonate 0A sulfate.
• a washing composition according to one of the Examples W1 to W17 contains 0.3 to 1.5% by weight of protease (375-1875 LVE/g.)
• a washing composition according to one of the Examples W1 to W17 contains 1.2% by weight of lipase (120 IE/g.)
• a washing composition according to one of the Examples W1 to W17 contains 0.4% by weight of protease (500 LVE/g.) 1.0% by weight of amylase (750 SKBE/g.)
• a washing composition according to one of the Examples W1 to W17 contains 2.0% by weight of amylase (1500 SKBE/g.)
• a washing composition according to one of the Examples W1 to W17 contains 0.2% by weight of protease (250 LVE/g.) 0.5% by weight of amylase (375 SKBE/ g.) 0.5 by weight of lipase lE/g.)
• a washing composition according to one of the Examples W1 to W17 contains 1.0% by weight of protea
• Example W18 The washing test is carried out with 18 washing composition according to the invention of the following composition:
• Fatty acid condensation product (according to Test Examples A to D) 10.0 ABS 10.0 KA-EO-sulfate 5.0 Soap 1822 3.0 Sodium tripolyphosphate 48.0 Na O.3.3SiO 4.5 CMC 1.5 Sodium sulfate and water Reminder
• the washing composition used in the control test B contains 10% by weight more sodium sulfate instead of the fatty acid condensation product.
• the average values were calculated from the estimations and are shown in the following table.
• the limiting values 1 and 6 were fixed as follows: samples of new cotton terry cloth were treated for 250 hours in an automatic washing machine under boiling wash conditions in water without additions. After drying the value 6 was given to the fabric pro-hardened in this way. Samples of new cotton terry cloth had the dressing removed and were treated with a solution of a di-tallow-alkyl-dimethyl ammonium chloride. The value 1 was given to the fabric softened in this way. Accordingly, the samples of the new untreated cotton terry cloth used in the test have handle values in the region 1.5-2.
• washing compositions according to the invention show their textile softening action specially on fine washing articles and easy-care textiles of cotton, polyester, polyacrylonitrile and polyamide, especially processed as woven and knitted fabrics, which are washed at 70 0, preferably -60" C.
• the Washing may also be carried out at higher temperatures, however, the textiles thus washed show after drying a remarkably pleasant and soft handle and, in the case of velvet textiles, a uniform pile.
• Already hardened fabric undergoes an excellent improvement in handle by washing with the washing composition according to the invention.
• An antistatic effect is imparted to the textiles by the treatment.
• compositions containing textile softeners consisting essentially of:
• customary surface-active compounds utilizable in neutral to alkaline textile washing baths selected from the group consisting of anionic surface-active compounds, amphoteric surface-active compounds, non-ionic surface-active compounds, and mixtures thereof, wherein not more than 50% by weight of said surface-active compounds are non-ionic surface-active compounds, and
• X is a member selected from the group consisting of hydroxyethyl, hydroxypropyl and dihydroxypropyl
• Y and Z are selected from the group consisting of hydrogen and X, with the proviso that at least one of Y and Z is hydrogen
• n is an integer from 1 to 3
• R is selected from the group consisting of hydrogen and alkyl and having 1 to 4 carbon atoms said textile softener higher fatty acid monoamide being the reaction product of 1 mol of said hydroxyalkylpolyamine with from 0.5 to 1.0 mols, calculated on the higher fatty acid content, of a higher fatty acid derivative selected from the group consisting of said higher fatty acids, lower alkyl esters of said higher fatty acids and said higher fatty acid triglycerides and said textile softener containing less than 5% by weight of fatty acid partial glycerides, and
• said customary surface-active compounds of component (1) (a) is a mixture of anionic surface-active compounds selected from the group consisting of surface-active sulfonates, surface-active sulfates and soap, and non-ionic surface-active compounds.
• compositions containing textile softeners consisting essentially of:
• anionic, non-ionic and amphoteric surface-active compounds selected from the group consisting of surface-active sulfonates and sulfates with from 8 to 18 carbon atoms in the hydrophobic moiety, soaps, and non-ionic surface-active polyethers, amineoxides, sulfoxides and phosphineoxides, wherein not more than 50% by weight of said surface-active compounds is said non-ionic surface-active compounds, and
• a non-surface-active foam inhibitor selected from the group consisting of N-alkylated-aminotriazines, N-alltylated chloroaminotriazines, aminotriazines containing polypropylene glycol or polybutylene glycol chains and chloroaminotriazines containing polypropylene glycol or polybutylene glycol chains, and
• enzymes selected from the group consisting of proteases, amylases, lipases and mixtures thereof wherein the enzymatic activity is in the range of 50 to 5000 LVE per gram of total washing agent in the case of proteases, of 20 to 5000 SKBE per gram of total washinging agent in the case of amylases and of 2 to 1000 IE per gram of total washing agent in the case of lipases.
• component (1) (a) the weight ratio of said surface-active sulfonates and sulfates to said soap is between :1 to 1:5.
• compositions containing textile softeners consisting essentially of:
• N-alkylated-aminotriazines selected from the group consisting of N-alkylated-aminotriazines, N-alkylated chloroaminotriazines, aminotriazines containing polypropylene glycol or polybutylene glycol chains and chloroaminotriazines containing polypropylene glycol or polybutylene glycol chains
• B 20% to by weight of inorganic builders, at least part of the builders being alkaline reacting, said builders weighing from 1 to 5 times that of component (A); and (C) 3% to 30% by weight of organic complexing compounds, whereby the total amount of said textile softening composition in said detergent composition is from 7.5 to 15% by weight.
• the detergent compositions of claim 16 having a content of enzymes wherein said enzymes are selected from the group consisting of proteases, amylases, lipases and mixtures thereof wherein the enzymatic activity is in the range of 50 to 5000 LVE per gram of total washing agent in the case of proteases, of 20 to 5000 SKBE per gram of total washing agent in the case of amylases and of 2 to 1000 IE per gram of total washing agent in the case of lipases.

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  • DK DK131638D patent/DK131638A/da unknown
• 1970
  • 1970-01-02 DK DK1870*#A patent/DK131638C/da active
  • 1970-01-06 NL NL7000104A patent/NL7000104A/xx not_active Application Discontinuation
  • 1970-04-16 US US29288A patent/US3704228A/en not_active Expired - Lifetime
  • 1970-04-29 GB GB2056470A patent/GB1313695A/en not_active Expired
  • 1970-06-04 FR FR7020510A patent/FR2045902A1/fr not_active Withdrawn
  • 1970-06-05 CH CH850570A patent/CH519021A/de not_active IP Right Cessation
  • 1970-06-05 BE BE751548D patent/BE751548A/xx unknown
  • 1970-06-05 AT AT506270A patent/AT300160B/de not_active IP Right Cessation
  • 1970-06-06 ES ES380482A patent/ES380482A1/es not_active Expired
  • 1970-06-08 JP JP45049429A patent/JPS4822802B1/ja active Pending

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