US3563902A - Detergents and cleansers - Google Patents

Detergents and cleansers Download PDF

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Publication number
US3563902A
US3563902A US683769A US3563902DA US3563902A US 3563902 A US3563902 A US 3563902A US 683769 A US683769 A US 683769A US 3563902D A US3563902D A US 3563902DA US 3563902 A US3563902 A US 3563902A
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United States
Prior art keywords
acid
detergent
agents
graying
salts
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Expired - Lifetime
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US683769A
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English (en)
Inventor
Edmund Schmadel
Walter Kling
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • 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
    • C11D3/3719—Polyamides or polyimides

Definitions

  • Novel detergent and cleansing agents are disclosed characterized by their ability to inhibit the graying of textile articles which takes place in laundering.
  • the novel detergent and cleaning agents are effective to prevent the graying of textile articles prepared at least in part with synthetic fibers.
  • the detergent and cleaning 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 polyamide, the acid and amide radicals of which respectively are derived from tricarboxylic and/or tetracarboxylic acids and diamines.
  • the detergent and cleaning agents contain the conventional surface active materials and the usual additives such as optical brighteners, bleaching agents, sudsers, anti-foamers, 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 polyamides.
  • 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.
  • carboxymethyleellulose 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 grayinhibiting 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 mixture, 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 water soluble salt of a free carboxyl group containing polyamide.
  • 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 polyamide, the acid radicals of which are derived from tricarboxylic and/or tetracarboxylic acids and the amide radicals of which are derived from compounds having two aliphatic amide groups.
  • Polyamides 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.
  • polyamide salts utilized in the formulation of the detergent compositions in accordance with the invention are prepared by known methods.
  • the starting materials for preparation of the free carboxyl group containing polyamide salts are aliphatic, cycloaliphatic and aromatic triand/or tetracarboxylic acids. Instances of preferred acids are citric acid, tricarballylic acid, nitrilo-triacetic acid, ethylenediaminotetraacetic acid, cyclohexanetricarboxylic acid, trimesic acid, oxytrimesic acid and pyromellitic acid.
  • the aforesaid acids can be replaced in amounts of up to 50 mole-percent by saturated or unsaturated aliphatic and cycloaliphatic acids or be aromatic dicarboxylic acids, such as for example malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid and by benzenedicarboxylic acids as well.
  • the polyvalent carboxylic acids that are suitable for use herein preferably contain 6 (citric acid) up to 20 carbon atoms.
  • the diamines which are employed in the preparation of the polyamides contain preferably 2 to 18 carbon atoms, may be straight-chained or branch-chained, saturated or unsaturated, aliphatic, cycloaliphatic or aromatic, and they may be interrupted by hetero atoms such as O, N and S.
  • suitable diamines include ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, pphenylene diamine, benzidene, piperazine, 4,4-diamin0- diphenylsulfone, and 4,4-diaminodiphenylether.
  • the preparation of the polyamides is carried out by the conventional method, as for example, by heating the mixture of acid and diamine for several hours in vacuo or in the presence of a solvent with which the water of reaction can be removed azeotropically by distillation.
  • a solvent with which the water of reaction can be removed azeotropically by distillation In place of the free di-, trior tetracarboxylic acids, their reactive derivatives such as for example, their anhydrides, can be also used as starting materials.
  • the molar ratio of the polycarboxylic acid to diamine within a preferred range of 0.9 to 1:1 to 1.1, it is possible to vary the degree of polymerization within certain limits. In the interest of a good anti-graying action, however, a high degree of polymerization is desirable. In order to prevent a premature interruption of chain formation, therefore, a molar ratio is preferred that is as close as possible to 1:1.
  • the polyamides containing free carboxyl groups which have been manufactured in the above-described manner are of a resin-like nature, substantially insoluble in water and in organic solvents, but easily soluble in dilute alkali lyes. They may also contain secondary amounts of amides of low molecular weight and of unrcacted starting materials 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 polyamides 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 polyamides can be added to the detergents in the form of their free acids, providing alkalinely reacting substances are present in a sufiiciently 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 a-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 a-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 detergent compositions 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-(methvlenenhosohonic id).
  • 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-(methvlenenhosohonic id
  • 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 detergent 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 polyamide 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.
  • 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.
  • the realistically simulated dust-sebum combination used for soiling the cotton yarn consisted of a mixture of kaolin, iron oxide black, carbon black and synthetic sebum (prepared from a mixture of A fatty acids, /3 fat and V3 hydrocarbons).
  • the cotton yarn contained approximately 11% pigments and 2% sebum after soiling.
  • the detergent which was used in the washing of these samples had the following composition: 20% n-dodecylbenzenesulfonate (sodium salt) to a polyamide content of 10 g./l. Appropriate amounts of this solution were added to the wash water.
  • the detergent which was used in these tests consisted of a liquid preparation having the following composition:
  • n-dodecylbenzenesulfonate (sodium salt) 1.1 g./l. coconut fatty alcohol sulfate (sodium salt) 1.1 g./l. tallow fatty alcohol sulfate (sodium salt) 16.0 g./l. sodium pyrophosphate 14.0 g./l. sodium sulfate 5.0 g./ l. graying inhibitor
  • 100 ml. of this stock solution was diluted to one liter with tap water of 10" dl-l. The samples were washed at 60 C. for 10 minutes with the Terg-O- Tometer operating at 100 r.p.m. The samples were then rinsed with distilled water three times, dried and photometrically evaluated.
  • Example 1 192 g. (1 mole) of anhydrous citric acid, 108 g. (1 mole) of hexamethylene diamine and 500 ml. of xylene were heated in a distillation apparatus which was provided with a system for separating the water and feeding back the solvent. The heating was continued until no further water of reaction separated in the receiver. The xylene was decanted from the insoluble resin that had been formed and the residue was dried in vacuo. The recovered polyamide dissolved when stirred in 2 N NaOH solution. The excess lye (about 5%) was neutralized with dilute sulfuric acid and the neutral solution was adjusted ing washings in each case. The washing tests with samples of polyamide fabrics were carried out by Method B (deposition method).
  • CMC Polyamlde, Perlon 1 CMC 70 64 55 51 1 73 67 55 60 2 72 65 58 54 3 70 65 58 55 4 74 71 63 6O 1
  • CMC designates carboxymethylcellulose (sodium salt) which was used for purposes of comparison.
  • a detergent composition consisting essentially of a detergent selected from the group consisting of anionic, ampholytic and non-ionic detergents, and mixtures thereof, and a graying inhibitor in an amount of from 0.1 to 20 weight percent based on total weight of the composition, said graying inhibitor being selected from the group consisting of water-soluble alkali metal and ammonium salts of a carboxyl group containing polyamide made by condensing with removal of water to a resin-like state substantially insoluble in xylene a polycarboxy'lic acid and a di amine in the ratio of 0.9 to 1.1 mole per mole (carboxylic acid group/amine group said polycarboxylic acid being selected from the group consisting of citric, tricarballylic, nitrilotriacetic, ethylenediaminotetracetic, cyclohexanetricarboxylic, trimesic; oxytrimesic and pyromellitic acids, and said diamine having in the range of 2 to 18 carbon atoms
  • composition of claim 1 wherein said diamine is selected from the group consisting of ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, p-p'henylene diamine, benzidene, piperazine, 4,4'-diaminodiphenylsulfone, and 4,4-di-aminodiphenylether.
  • composition of claim 1 wherein up to 50 mole percent of said polycarboxylic acid is replaced in poly- 7 amide by the addition of 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Detergent Compositions (AREA)
US683769A 1966-11-19 1967-11-17 Detergents and cleansers Expired - Lifetime US3563902A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEH0061039 1966-11-19

Publications (1)

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US3563902A true US3563902A (en) 1971-02-16

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US (1) US3563902A (de)
AT (1) AT273340B (de)
BE (1) BE706664A (de)
CH (1) CH494276A (de)
DD (1) DD64536A (de)
DE (1) DE1617121C3 (de)
DK (1) DK125901B (de)
ES (1) ES347353A1 (de)
GB (1) GB1200115A (de)
NL (1) NL6714292A (de)
NO (1) NO122200B (de)
SE (1) SE330584B (de)
ZA (1) ZA6706930B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887480A (en) * 1972-09-08 1975-06-03 Economics Lab Detergent compositions and methods of making and using them
US4021377A (en) * 1973-09-11 1977-05-03 Miles Laboratories, Inc. Liquid detergent composition
US4735746A (en) * 1986-06-16 1988-04-05 Texaco Inc. Long lasting detergent bar containing a polyamide or polyester polymer
US5139706A (en) * 1990-05-14 1992-08-18 Texaco Chemical Company Fatty amides prepared by reacting dicarboxylic acids, polyoxyalkylene amine bottoms products and fatty acids or esters thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2695638B1 (fr) * 1992-09-15 1995-04-07 Rhone Poulenc Chimie Procédé de préparation de l'acide L-aspartique via l'aspartate d'ammonium.
FR2696473A1 (fr) * 1992-10-06 1994-04-08 Rhone Poulenc Chimie Composition détergente incorporant un biopolymère polyimide hydrolysable en milieu lessiviel.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887480A (en) * 1972-09-08 1975-06-03 Economics Lab Detergent compositions and methods of making and using them
US4021377A (en) * 1973-09-11 1977-05-03 Miles Laboratories, Inc. Liquid detergent composition
US4735746A (en) * 1986-06-16 1988-04-05 Texaco Inc. Long lasting detergent bar containing a polyamide or polyester polymer
US5139706A (en) * 1990-05-14 1992-08-18 Texaco Chemical Company Fatty amides prepared by reacting dicarboxylic acids, polyoxyalkylene amine bottoms products and fatty acids or esters thereof

Also Published As

Publication number Publication date
BE706664A (de) 1968-05-17
DK125901B (da) 1973-05-21
DE1617121A1 (de) 1971-02-18
AT273340B (de) 1969-08-11
NL6714292A (de) 1968-05-20
DD64536A (de)
SE330584B (de) 1970-11-23
NO122200B (de) 1971-06-01
CH494276A (de) 1970-07-31
DE1617121B2 (de) 1974-12-05
DE1617121C3 (de) 1975-07-31
GB1200115A (en) 1970-07-29
ES347353A1 (es) 1969-05-16
ZA6706930B (de)

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