US3211658A - Detergent composition with improved bleaching efficiency - Google Patents

Detergent composition with improved bleaching efficiency Download PDF

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Publication number
US3211658A
US3211658A US179197A US17919762A US3211658A US 3211658 A US3211658 A US 3211658A US 179197 A US179197 A US 179197A US 17919762 A US17919762 A US 17919762A US 3211658 A US3211658 A US 3211658A
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US
United States
Prior art keywords
perborate
copper
acid
detergent composition
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US179197A
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English (en)
Inventor
Jean Hirtz
Gilles Noiriel
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication of US3211658A publication Critical patent/US3211658A/en
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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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/021—Sealings between relatively-stationary surfaces with elastic packing

Definitions

  • suostantially 1 58 dry denotes a flowable particulate apparently dry solid DETERGENT COMPOSITION WITH IMPROVED BLEACHING EFFICIENCY Jean Lucien Hirtz, Suresnes, and Gilles noisyriel, Puteaux,
  • the present invention relates to an improved method ment are not those encountered during the washing, but of laundering at the boil and to detergent compositions represent a Standard for indicating and determining the the fo having h d bl hi fli i appropriate dissociation constants which will enable the Detergent compositions previously proposed for skilled worker to choose the desired sequestering agents laundering t h b il are complex mixtures comprising for the detergent compositions of this invention.
  • the perborate most generthe P of the Invention include the Soaps, Such as the ally employed is sodium perborate, in amounts of between 40 water-soluble salts of higher fatty acids or rosin acids 5 and 30% by weight f the detergent mixture such as may be derived from fats, oils and waxes of However, the perborate not only oxidizes the coloring ammal, vegetable or marine Origin.
  • morgamc copper i
  • Stable the hresehce of sald sulfuric acid esters of polyhydric alcohols incompletely herhorath h forms a complex whh copher esterified with higher fatty acids, e.g.
  • coconut oil mono comprising a dissociation constant the common logar1thm of glyceride munosulfate, tanow diglyceride monosulfate; which 15 between about and Said copper Salt and the hydroxy sulfonated higher fatty acid esters such and sequestering agent bcing Present in amounts sufiicient as the higher fatty acid esters of low molecular weight to enhance the bleaching action of the perborate at the boil.
  • alkylol sulfonic acids e.g. oleic acid ester of isethionic acid.
  • Suitable non-ionic surface active agents are well known to the art and include such agents as the condensation products of alkyl phenols with ethylene oxide, e.g. the reaction product of isoctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; condensation products of tall oil with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate; the condensation products of polypropylene glycol with ethylene oxide; and the higher fatty acid alkylolamides, eg the diethanolamide of coconut oil fatty acids.
  • the concentration of detergent in the inventive com positions will generally range from 4 to by weight.
  • Substantial amounts of compatible builder materials will also be usually present, i.e. of the order of between about 40 to 90% by Weight of the detergent composition.
  • the builders particularly suitable for the compositions of this invention are water soluble inorganic salts such as sodium sulfate, sodium chloride, sodium tripolyphosphates, sodium pyroand ortho-phosphates, sodium carbonate and the like.
  • the perborate bleaching agent preferably employed in the compositions of this invention is sodium perborate and more particularly sodium perborate tetrahydrate, though it will be understood that other perborates can be employed as the bleach.
  • copper sulfate is preferably employed as the catalytic agent, any water-soluble copper salt will serve, as for example, the highly soluble nitrate or acetate salts.
  • sequestering agents which will form a complex with copper having the essential dissociation constants are methylaminodiacetic acid, aminotriacetic acid and hydroxyethylaminodiacetic acid. These agents form complexes with copper having the following dissociation constants expressed in (logarithms).
  • Dissociation constant Agent of copper complex Methylaminodiacetic acid 11.09 Aminotriacetic acid 12.68 Hydroxyethylaminodiacetic acid 11.90
  • ATA aminotriacetic acid
  • the pH of the present detergent compositions will normally be in the range from 8-11.5 and that, therefore, the sequestering agents are probably present in the detergent composition as salts. It is to be also understood that strong sequestering agents such as EDTA cannot be effectively employed in the compositions of this invention. This is because EDTA forms a complex with copper having a dissociation constant of 18.5 which is too high, and hence unsatisfactory, for the practice of this invention.
  • the content of perborate can be diminished relatively to that of comparable detergent compositions containing strong sequestering agents such as EDTA.
  • the amounts of perborate can be reduced to 5% by weight of the entire composition without experiencing any diminution in bleaching effect in comparison to comparable compositions which contain 10% perborate but lack the instant combination of copper salt and indicated sequestrant.
  • compositions containing 10% perborate in combination with 0.2% EDTA by weight without copper salt offer no greater bleaching efficiency than compositions containing 3% perborate, 0.4% ATA and 0.02% by weight anhydrous copper sulfate.
  • the amount of copper salt in the detergent composition of this invention must be such that the composition contains from about 30 to about 300 p.p.m. (parts per million) of copper and preferably from 40 to p.p.m.
  • the associated amount of sequestering agent should be such'that about 3 to 15 molecules and preferably 10 to 13, thereof, should be present per atom of copper in the detergent composition.
  • compositions of this invention can be prepared in any suitable manner such as, e.g., by spray drying the detergent mixture, the mineral salts, and the copper salt, and then adding, by dry mixing, the perborate and the sequestering agent as well as those constituent which could be sensitive to heat, such as perfume.
  • the bleaching efficiency percentage of the compositions of this invention is determined as follows:
  • Samples of cotton fabric are dyed by means of an oxidizible dye and washed with a bleach-free organic detergent until the complete removal of the excess of dye.
  • These dyed fabrics having a reflectance on a Hunter colorimeter in the range of 20, are washed with a detergent composition containing an organic detergent and a persalt, in glass beakers, for the time intervals and at temperatures used in a normal washing at the boil.
  • the persalt partly oxidizes the dye and after washing, the fabric is lighter than at the start.
  • the reflectance of the fabric is measured by means of a Hunter photocolorimiter equipped with a green filter.
  • the reflectance may be represented as BD before dyeing, BW before washing, and AW after washing.
  • the bleaching efiiciency, in percent, is then 100 (AW-BW) divided by (BDBW).
  • Water-soluble organic anionic or nonionic detergent Synthetic detergent, soap or their mixtures 4 to 40%.
  • Water-soluble inorganic salts 40 to Perborate, especially sodium 3 to 20%.
  • Water-soluble copper salt in an amount corresponding in relation to the entire composition of 30 to 300 p.p.m. of Cu (003% to .03%).
  • sequestering agent which forms a copper complex having a dissociation constant the common logarithm of which is between -11 and 15, in an amount corresponding for each atom of Cu, of 3 to 15 molecules.
  • Perfume, coloring matter, blueing agent 0 to 1%.
  • a basic detergent composition is made of the following formulation:
  • Washing solutions are prepared by dissolving 12.5 grams or 5 grams per liter of the above basic detergent composition in aqueous washing mediums. Washing is then carried out at the boil and the results noted using each solution.
  • washing solutions are prepared in like manner but with the difference that methylaminodiacetic acid, hydroxyethylaminodiacetic acid or aminotriaoetic acid sequestrants are separately added to the basic detergent compositions at concentrations of 0.2% by weight of the basic detergent composition.
  • EXAMPLE 5 Another detergent composition of the subject invention is made of the following formulation. It also exhibits enhanced bleaching action at the boil.
  • EXAMPLE 2 Sodium dodecylbenzene sulfonate 8%. To separate portions of the basic detergent formula- 40 g i salt of sulfated lauryl alco 87 tion indicated in Example 1, there are added 0.2% by M o 15"";"75'"; weight EDTA or 0.4% ATA and 0.02% anhydrous copper g #3" e 3 7 sulfate. To a similar third basic formulation but having ty 'm-"i a perborate concentration of only 6% by Weight there iS i yp 05p g also added 0.4% ATA and 0.02% of copper sulfate. P? Y rate Sodium silicate 7%.
  • Example 11 These formulations are then dissolved as in Example 1, to form washing solutions.
  • the bleaching efliciency of each solution is observed and tabulated in Table 11 be low.
  • Copper sulfate in an amount corre- Copper acetate in an amount corresponding in relation to the entire composition of p.pm. of Cu. Hydroxyethylaminodiacetic acid in an amount corresponding for each atom of Cu of l0 molecules.
  • Fluorescent dye, perfume, sodium sulfate and moisture Balance to EXAMPLE 6 The following formulation also exhibits enhanced bleaching action at the boil.
  • a stable, substantially dry, perborate-containing detergent composition effective for washing at the boil consisting essentially of by weight from about 4 to 40% of a member selected from the group consisting of water-soluble, synthetic, non-soap anionic and nonionic organic detergents, from about 3 to about 20% watersoluble inorganic perborate, from about 40 to about 90% water-soluble inorganic alkali metal non-oxidizing builder salts, a water-soluble inorganic copper salt, and a sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid, and bydroxyethylaminodiaeetic acid, the copper salt being present in amount sufficient to produce a copper atom concentration of from about 30 to 300 parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 3 to 15 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.
  • composition according to claim 1 in which the perborate is sodium perborate tetrahydrate and the water-soluble copper salt is copper sulfate.
  • a stable substantially dry perborate-containing detergent composition effective for washing at the boil consisting essentially of by weight from 4 to 40% of a sodium salt of a higher alkyl benzene sulfonate containing from 10 to 16 carbon atoms in the alkyl group, from 3 to 20% sodium perborate tetrahydrate, from 40 to 90% water-soluble inorganic alkali metal non-oxidizing builder salts, copper sulfate and a sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid, and hydroxyethylaminodiacetic acid, the copper salt being present in amount suflicient to produce a copper atom concentration of from 40 to parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 10 to 13 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.
  • a stable substantially dry perborate-containing detergent composition effective for washing at the boil consisting essentially of by weight about 22% sodium dodecylbenzene sulfonate, about 30% sodium tripolyphosphate, about 2.5% monoethanolamide of coconut oil fatty acid, about 7% sodium silicate, about 1% magnesium silicate, about 10% hydrated sodium perborate, copper sulfate and sequestering agent selected from the group consisting of methylaminodiacetic acid, aminotriacetic acid and hydroxyethylaminodiacetic acid, the copper sulfate being present in amount sufficient to produce a copper atom concentration of from 40 to 80 parts per million parts by weight of the detergent composition, and the sequestering agent being present in amount such that 10 to 13 molecules thereof are contained in the detergent composition per atom of copper, said amounts of copper salt and sequestering agent enhancing the bleaching action of the perborate at the boil.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
US179197A 1961-03-24 1962-03-12 Detergent composition with improved bleaching efficiency Expired - Lifetime US3211658A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR856728A FR1338856A (fr) 1961-03-24 1961-03-24 Composition détergente à effet de blanchiment amélioré

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US3211658A true US3211658A (en) 1965-10-12

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US (1) US3211658A (d)
AU (1) AU268224B2 (d)
BE (1) BE614629A (d)
CH (1) CH404054A (d)
DK (1) DK110214C (d)
FR (1) FR1338856A (d)
GB (1) GB984459A (d)
NL (2) NL146531B (d)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3383319A (en) * 1965-10-22 1968-05-14 Motorola Inc Cleaning of semiconductor devices
US3398096A (en) * 1964-07-24 1968-08-20 Lever Brothers Ltd Low temperature bleaching composition
US3488288A (en) * 1968-03-04 1970-01-06 Peter Strong & Co Inc Denture cleansers
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3901819A (en) * 1972-09-14 1975-08-26 Kao Corp Compositions for activating an inorganic peroxide bleaching agent
US3969257A (en) * 1971-07-23 1976-07-13 Colgate-Palmolive Company Washing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
US3991000A (en) * 1973-12-11 1976-11-09 Colgate-Palmolive Company Built bleaching detergent
US4680131A (en) * 1983-04-20 1987-07-14 The Proctor & Gamble Company Detergent compositions
US6369288B1 (en) 2000-01-05 2002-04-09 The United States Of America As Represented By The Secretary Of The Navy Chemical and biological warfare decontaminating solution using bleach activators
WO2003014283A1 (en) * 2001-08-02 2003-02-20 Unilever Plc Laundry detergent compositions
WO2010084351A1 (en) * 2009-01-26 2010-07-29 Innospec Limited Chelating agents and methods relating thereto

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT7925699A0 (it) * 1978-09-14 1979-09-12 Eastman Kodak Co Composizioni fotografiche di sbianca, e metodi per trattamento fotografico.
GR76237B (d) 1981-08-08 1984-08-04 Procter & Gamble
US4481129A (en) * 1981-12-23 1984-11-06 Lever Brothers Company Bleach compositions
US4488980A (en) * 1982-12-17 1984-12-18 Lever Brothers Company Detergent compositions
US4478733A (en) * 1982-12-17 1984-10-23 Lever Brothers Company Detergent compositions
GB8312185D0 (en) * 1983-05-04 1983-06-08 Unilever Plc Bleaching and cleaning composition
GB8329762D0 (en) * 1983-11-08 1983-12-14 Unilever Plc Manganese adjuncts
GB8331278D0 (en) * 1983-11-23 1983-12-29 Unilever Plc Detergent composition
ES2008833A6 (es) * 1988-10-25 1989-08-01 Camp Jabones Composiciones blanqueantes para materias textiles yno celulosicas con alta efectividad a bajas temperaturas, y procedimiento de blanqueo con las mismas.
GB8908416D0 (en) * 1989-04-13 1989-06-01 Unilever Plc Bleach activation
AU1493392A (en) * 1991-08-06 1993-02-11 W.R. Grace & Co.-Conn. Biodegradable bleach stabilizers for detergents
US7044985B2 (en) 1999-12-21 2006-05-16 Clariant Finance (Bvi) Limited Process for pre-treating cellulosic fibers and cellulosic fiber blends

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2240957A (en) * 1935-10-30 1941-05-06 Gen Aniline & Film Corp Process for avoiding and rendering harmless the precipitates of water insoluble metal salts
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2542385A (en) * 1946-10-12 1951-02-20 Gen Aniline & Film Corp Detergent composition
GB765750A (en) * 1954-06-21 1957-01-09 Hedley Thomas & Co Ltd Detergent compositions
US2975139A (en) * 1956-10-02 1961-03-14 Fmc Corp Laundering method and composition therefor
US3156654A (en) * 1961-06-19 1964-11-10 Shell Oil Co Bleaching

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2240957A (en) * 1935-10-30 1941-05-06 Gen Aniline & Film Corp Process for avoiding and rendering harmless the precipitates of water insoluble metal salts
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2542385A (en) * 1946-10-12 1951-02-20 Gen Aniline & Film Corp Detergent composition
GB765750A (en) * 1954-06-21 1957-01-09 Hedley Thomas & Co Ltd Detergent compositions
US2975139A (en) * 1956-10-02 1961-03-14 Fmc Corp Laundering method and composition therefor
US3156654A (en) * 1961-06-19 1964-11-10 Shell Oil Co Bleaching

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3398096A (en) * 1964-07-24 1968-08-20 Lever Brothers Ltd Low temperature bleaching composition
US3383319A (en) * 1965-10-22 1968-05-14 Motorola Inc Cleaning of semiconductor devices
US3532634A (en) * 1966-03-01 1970-10-06 United States Borax Chem Bleaching compositions and methods
US3488288A (en) * 1968-03-04 1970-01-06 Peter Strong & Co Inc Denture cleansers
US3969257A (en) * 1971-07-23 1976-07-13 Colgate-Palmolive Company Washing and bleaching composition containing bleach, activator and a nitrilotricarboxylic acid compound
US3901819A (en) * 1972-09-14 1975-08-26 Kao Corp Compositions for activating an inorganic peroxide bleaching agent
US3991000A (en) * 1973-12-11 1976-11-09 Colgate-Palmolive Company Built bleaching detergent
US4680131A (en) * 1983-04-20 1987-07-14 The Proctor & Gamble Company Detergent compositions
US6369288B1 (en) 2000-01-05 2002-04-09 The United States Of America As Represented By The Secretary Of The Navy Chemical and biological warfare decontaminating solution using bleach activators
WO2003014283A1 (en) * 2001-08-02 2003-02-20 Unilever Plc Laundry detergent compositions
US20040180803A1 (en) * 2001-08-02 2004-09-16 Sarah Dixon Laundry detergent compositions
WO2010084351A1 (en) * 2009-01-26 2010-07-29 Innospec Limited Chelating agents and methods relating thereto
US8801962B2 (en) 2009-01-26 2014-08-12 Innospec Limited Chelating agents and methods relating thereto

Also Published As

Publication number Publication date
GB984459A (en) 1965-02-24
BE614629A (d)
AU1552962A (en) 1963-09-26
FR1338856A (fr) 1963-10-04
AU268224B2 (en) 1966-06-17
NL146531B (nl) 1975-07-15
CH404054A (fr) 1965-12-15
DK110214C (da) 1971-01-18
NL276367A (d)

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