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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates

Definitions

• Novel detergent and cleansing agents are disclosed characterized by their ability to inhibit the graying of textile articles which takes place in laundering.
• novel detergent and cleansing agents are effective to prevent the graying of textile articles prepared at least in part with synthetic fibers.
• the detergent and cleansing agents of the invention are characterized by a content of 0.1 to 20 wt. percent referred to the total composition of at least one water soluble salt of a free carboxyl group containing polyester, the acid and alcohol radicals of which respectively are derived from tricarboxylic and/or tetracarboxylic acids and bivalent alcohols.
• the detergent and cleaning agents contain the conventional surface active materials and the usual additives such as optical brighteners, bleaching agents, sudsers, antifoamers, etc.
• This invention relates to detergent and cleaning agents characterized by their ability to inhibit the graying of textile articles in laundering.
• this invention relates to detergent and cleaning agents containing water-soluble salts of freecarboxyl group containing polyesters.
• graying inhibitors prevent a resorption of the dissolved dirt onto the cleaned surfaces.
• These substances are usually polyanionic polymers which are manufactured from natural substances such as cellulose, gelatins or glue, or are prepared by the polymerization of vinyl compounds, such as acrylic acid, methacrylic acid, maleic acid and mixtures thereof with copolymerizable olefins. Further, the polysulfonates of vinyl polymers have already been proposed as useful gray-inhibiting additives for detergent and cleanser preparations.
• carboxymethylcellulose has achieved any great technical importance, inasmuch as its gray-inhibiting action excels that of any synthetic polymers that have become known.
• carboxymethylcellulose as well as the above-named synthetic polymers have the disadvantage that their gray-inhibiting action is limited to cellulose fibers, whereas they are practically ineffectual in the washing of synthetic fiber material, particularly materials prepared from polyamides, polyesters and polyolefins. This disadvantage is particularly noticeable in connection with white textiles made of synthetic fibers'or mixed fabrics made of synthetic and cellulose fibers, i.e., polyester-cotton mixtures, which turn irreversibly gray in use despite repeated washing and thus become unattractive and must be discarded.
• Another object is to provide improved detergent compositions containing as the gray-inhibiting agent, a watersoluble salt of a free carboxyl group containing polyester.
• a yet further object is to provide improved gray-inhibiting detergent compositions which are surprisingly effective in laundering textile articles prepared at least in part with synthetic fibers.
• detergent compositions comprising a detergent surfactant compound and as a graying inhibitor 0.1 to 20 wt. percent referred to the total detergent compositions of a free carboxyl group containing polyester, the acid radicals of which are derived from tricarboxylic and/or tetracarboxylic acids'and the alcohol radicals of which are derived from compounds having two aliphatic hydroxyl groups.
• Polyesters can also be used to produce the same effect in which up to 50 mole percent of the trior tetracarboxylic acid radicals have been replaced by dicarboxylic acid radicals.
• polyester salts as used in the detergent compositions of the invention are manufactured by prior-art methods.
• the starting materials are aliphatic, cycloaliphatic and aromatic tricarboxylic and tetracarboxylic acids and mixtures thereof.
• suitable acids are citric acid, tricarballylic acid, nitrilotriacetic acid, ethylenediaminotetracetic acid, cyclohexanetricarboxylic acid, trimesic acid, oxytrimesic acid and pyromellitic acid.
• the aforesaid acids may be replaced in amounts of up to 50 mole percent, by saturated or unsaturated aliphatic, cycloaliphatic or aromatic dicarboxylic acids, such as for example, malonic, succinic, glutaric, adipic, sebacic, maleic and fumaric acid, as well as by benzenedicarboxylic acids.
• the polyvalent carboxylic acids used generally contain 6 (citric-see examples) up to 20 carbon atoms.
• the compounds having two aliphatic hydroxyl groups may contain aliphatic, cycloaliphatic, araliphatic, straight-chain or branched, saturated or unsaturated hydrocarbon radicals as well as hetero atoms such as O, N and S.
• Suitable hydroxyl compounds are aliphatic diols having 2 to 18, preferably 2 to 8 carbon atoms such as for example ethylene glycol, propanediol-1,3, propanediol-l,2, butanediol-1,3, hexanediol-l,6, heptanediol-l,7, and 2,2-diethylpropanediol-l,3; ether alcohols such as dior tripropylene glycol, glycerine monoalkyl ether and thiodiethylene glycol.
• Illustrative of the starting substances having cyclic hydrocarbon radicals are the following: cyclohexanediol and those bivalent phenols,
• the hydroxyl groups of which are etherified with aliphatic radicals contain 1 to 6, preferably 1 to 3, carbon atoms, and the alkyl, aryl or alkylaryl radicals contain up to 18 carbon atoms.
• Such compounds include, for example, N-methyldiethanolamine, N-methyldipropanolamine, N- ethyldiethanolamine, N-butyldiethanolamine, N-dodecyldiethanolamine, N-cyclohexyldipropanolamine and N- phenyldiethanolamine.
• the preparation of the polyesters is carried out by the conventional methods, as for example, by heating the mixture of starting materials for several hours under normal pressure or in vacuo, in the presence in either case of a solvent with which the water of reaction can be removed azeotropically by distillation.
• the reaction can be accelerated by the addition of common esterification catalysts, especially strong inorganic or organic acids.
• common esterification catalysts especially strong inorganic or organic acids.
• the anhydrides and halides of these acids can also be used as starting materials. Particularly suitable in this connection are the dihalides.
• the polyvalent carboxylic acids in the form of their diesters derived from univalent alcohols of low molecular weight, can be re-esterified with the bivalent alcohols in the presence of known reesterification catalysts, in the conventional manner.
• diesters are citric acid dimethyl ester and pyromellitic acid diethyl ester. If alkaline re-esterification catalysts are used, care must be taken to see that they are still present in sufiicient excess after the neutralization of the free carboxyl groups.
• a molar ratio of polycarboxylic acid to bivalent alcohol within a preferred range of l.l::9 to 0.9: 1.1, it is possible to vary the degree of polymerization within certain limits. In the interest of a good anti-graying action, a high degree of polymerization is desirable. To prevent a premature interruption of chain formation, therefore, a molar ratio is preferred that is as close as possible to 1:1.
• polyesters containing free carboxyl groups and manufactured in the above-described manner are of a resin-like nature, substantially insoluble inwater and in organic solvents, but easily soluble in dilute alkali lyes. They may also contain secondary amounts of esters of low molecular weight and of unreacted starting substances which can be removed by extraction with organic solvents and thereafter recycled for further reaction. As these compounds, however, do not impair the cleaning properties of the agents, such separation is generally unnecessary.
• the detergents may contain the polyesters according to the invention in the form of any of their water-soluble salts and preferably in the form of their alkali metal and ammonium salts.
• ammonium salts is intended also to include the salts of the polyesters with organic ammonium bases.
• the polyesters can be added to the detergents in the form of their free acids, providing alkalinely reacting substances are present in a sufficiently great excess for the formation of salts.
• the new detergents and cleansing agents contain the surface-active substances customarily used in such agents, such as those of the sulfate or sulfonate type, for example, the primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated fatty alcohols, and alkylbenzenesulfonates, primary and secondary olefin sulfonates, alkyl sulfonates and u-sulfofatty esters.
• the surface-active substances customarily used in such agents such as those of the sulfate or sulfonate type, for example, the primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated fatty alcohols, and alkylbenzenesulfonates, primary and secondary olefin sulfonates, alkyl sulfonates and u-sulfofatty esters.
• Additional compounds of this class which may be 'used are the high molecular weight sulfatized partial ethers and partial esters of polyvalent alcohols; the sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols; fatty acid taurides and fatty acid isoethionates and homologues thereof. Also suitable are the alkali soaps of fatty acids as well as the fatty acid condensation products of amino acids or degraded proteins; and ampholytes such as alkylbetaines and alkylsulfobetaines.
• the agents can furthermore contain non-ionic wash-active substances, such as alkyl and acyl polyglycolethers, co'condensation products of polyethylene glycol and polypropylene glycol, fatty acid sugar esters, aminoxides and fatty acid alkanolamides. Any of the foregoing compounds can also be used in the form of mixtures thereof. If the compounds have an aliphatic hydrocarbon radical, the latter is preferably to be straight-chained and have 8 to 22 carbon atoms. In compounds having araliphatic hydrocarbon radicals, the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms.
• the new detergents and cleansers can contain other conventional components such as pyrophosphates, polyphosphates and the more highly condensed phosphates, as well as silicates, in the form of their alkali salts; oxygen-yielding bleaches or bleaches containing active chlorine, such as alkali perborates, alkali percarbonates, alkali hypochlorites, chlorinated cyanuric acids and their alkali salts; as well as neutral salts such as magnesium silicate and sodium sulfate.
• active chlorine such as alkali perborates, alkali percarbonates, alkali hypochlorites, chlorinated cyanuric acids and their alkali salts
• neutral salts such as magnesium silicate and sodium sulfate.
• sequestering agents may be present, particularly alkali salts of aminopolycarboxylic acids, e.g., the sodium salts of aminotriacetic acid or of ethylenediaminotetraacetic acid and the alkali salts of hydroxyalkyldiphosphonic acids and aminopolyphosphonic acids, such as the disodium salt of l-hydroxyethane-l,l-diphosphonic acid or the hexasodium salt of aminotri-(methylenephosphonic acid).
• alkali salts of aminopolycarboxylic acids e.g., the sodium salts of aminotriacetic acid or of ethylenediaminotetraacetic acid
• the alkali salts of hydroxyalkyldiphosphonic acids and aminopolyphosphonic acids such as the disodium salt of l-hydroxyethane-l,l-diphosphonic acid or the hexasodium salt of aminotri-(methylenephosphonic acid).
• Substances for the regulation of the pH can also be components of the mixture. These include sodium carbonate, sodium bicarbonate, lactic acid and citric acid and the like.
• the detergents can also contain optical brighteners, such as the derivatives of diaminostilbenedisulfonic acid or of diarylpyrazolinesulfonic acid.
• optical brighteners such as the derivatives of diaminostilbenedisulfonic acid or of diarylpyrazolinesulfonic acid.
• the detergents may contain suds improvers, such as fatty acid amides, or anti-foaming agents, particularly trialkylmelamines.
• the new detergents and cleansers may be in solid form, and preferably powder form, or in the form of solutions or pastes. Because of the excellent water solubility of the polyester salts they are particularly well suited for the manufacture of liquid detergent concentrates.
• Such liquid preparations may contain, in addition, to the above-named components, hydrotropic substances such as alkylbenzenesulfonates of low molecular weight, urea, and organic solvents.
• the cleansing action can be further improved by the addition of standard graying inhibitors, particularly carboxymethylcellulose.
• standard graying inhibitors particularly carboxymethylcellulose.
• the amounts of carboxymethylcellulose to be used will be approximately from 0.1 to 3% of the total weight of the detergents.
• the new detergents of the invention are suitable for the cleaning of articles of all kinds, but particularly for the washing of textiles which are made of synthetic fibers, cellulose fibers, regenerated cellulose, or of mixtures of the aforesaid types of fibers.
• the new detergents make the washing process itself easier and improve the whiteness of the laundry.
• CMC as used hereinafter 0% graying inhibitor 40 designates carboxymethylcellulose, which was used in 35 25% sodium sulfa each case as comparison substance. 7
• the cotton samples were washed at 90 C. for 30 minutes at a goods-to-wash-water ratio TABLE I of 1:12 (wash water lfS ml,), and the synthetic fabric i ill lgi samples were washed at C. for 30 minutes at a goodslfihibitolr a nt l atlor i l glz to-wash-water ratio of 1:30 (wash water 290 ml.).
• the detergent which was used in these tests consisted of Percent reflectance at l7l:lld/lprC1il::,adl.lOn1b:3Vlng K3111: follonliicomptiztlon.
• graying inhibitor in an amount from 0.1 to 20 weight percent based on the total weight of said composition, said graying inhibitor being selected from the group consisting of the alkali metal and ammonium salts of aresin-like, water and xylene insoluble, polyester containing free-carboxyl groups, the acid radical of said polyester being derived from a polyvalent carboxylic acid selected from the group consisting of citric, tricarballylic, nitrilotriacetic, ethylene diaminotetracetic, cyclohexanetriacetic, trimesic, oxytrimesic and pyromellitic acids, and the'alcohol radical of said polyester being derived from a bivalent alcohol from the group consisting of bivalent aliphatic alcohols and amino alcohols, said aliphatic alcohols containing 2 to 18 carbon atoms in the molecule and said amino alcohols being substituted at the nitrogen atom thereof by an alkyl radical having
• composition of claim 1 wherein said bivalent alcohol is selected from the group consisting of ethylene glycol, hexanediol and N-dodecyldiethanolamine.
• composition of claim 1 wherein up to 50 mol percent of said polyvalent carboxylic acid reacting with said bivalent alcohol is replaced with a dicarboxylic acid selected from the group consisting of malonic, succinic, glutaric, adipic, sebacic, maleic and fumaric acids.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Polyesters Or Polycarbonates (AREA)
• Ship Loading And Unloading (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=7161240

Family Applications (1)

Country Status (12)

Cited By (6)

Families Citing this family (2)

• 0
  • DD DD63599D patent/DD63599A/xx unknown
• 1966
  • 1966-11-19 DE DE1617122A patent/DE1617122C3/de not_active Expired
• 1967
  • 1967-06-29 SE SE09679/67*A patent/SE330585B/xx unknown
  • 1967-10-20 NL NL676714291A patent/NL151129B/nl unknown
  • 1967-11-17 CH CH1611167A patent/CH495422A/de not_active IP Right Cessation
  • 1967-11-17 GB GB45770/67A patent/GB1196173A/en not_active Expired
  • 1967-11-17 US US683778A patent/US3563903A/en not_active Expired - Lifetime
  • 1967-11-17 DK DK576867AA patent/DK125902B/da unknown
  • 1967-11-17 AT AT1037167A patent/AT274184B/de active
  • 1967-11-17 BE BE706662D patent/BE706662A/xx unknown
  • 1967-11-18 ES ES347352A patent/ES347352A1/es not_active Expired
  • 1967-11-18 NO NO170595A patent/NO122199B/no unknown

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