US3811833A - Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith - Google Patents

Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith Download PDF

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Publication number
US3811833A
US3811833A US00268051A US26805172A US3811833A US 3811833 A US3811833 A US 3811833A US 00268051 A US00268051 A US 00268051A US 26805172 A US26805172 A US 26805172A US 3811833 A US3811833 A US 3811833A
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United States
Prior art keywords
hydrogen peroxide
percent
bleaching
composition
salt
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Expired - Lifetime
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US00268051A
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English (en)
Inventor
N Stalter
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EIDP Inc
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EI Du Pont de Nemours and Co
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US00268051A priority Critical patent/US3811833A/en
Priority to CA173,982A priority patent/CA1003605A/en
Priority to IT26029/73A priority patent/IT990818B/it
Priority to FR7323905A priority patent/FR2190912B1/fr
Priority to BE132921A priority patent/BE801681A/xx
Priority to DE19732333201 priority patent/DE2333201A1/de
Priority to JP48073343A priority patent/JPS4952784A/ja
Priority to GB3149373A priority patent/GB1419184A/en
Application granted granted Critical
Publication of US3811833A publication Critical patent/US3811833A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

  • ABSTRACT A stable aqueous bleaching composition comprising: (1) concentrated, acidic hydrogen peroxide stabilized with a stannate salt; (2) an ammonium salt; (3) a stabilizing amount of an organic acid, preferably an alkylidene diphosphonic acid or salt; (4) optionally, other additives.
  • the bleaching composition alkaline, the Nl-l, ion is converted to ammonium hydroxide, which promotes the bleaching activity of hydrogen peroxide.
  • hydrogen peroxide has long been known as a bleaching agent, it has never achieved significant acceptance for laundry usage and no hydrogen peroxide composition formulated for laundry bleaching usage, either domestic or industrial, is available commercially today. This is so notwithstanding the advantages which a liquid hydrogen peroxide bleach offers: convenient liquid form, ideal for use in cold water, compatible with all fabrics, effective on permanent-press finishes, compatible with most fabric softeners, certain germicides, and optical dyes, and satisfactory economics.
  • the failme of hydrogen peroxide to find use as a laundry bleach is attributable in large measure to the fact that no chemical prmoting agent was available which could be formulated into the hydrogen peroxide solution by the manufacturer without causing precipitation of the stannate salts commonly used to stabilize acidic hydrogen peroxide as produced.
  • the invention also includes a process for bleaching comprising admixing the bleaching composition with an alkalining agent in such quantity as to make the pH of the resulting admixture greater than 7.0 diluting the admixture to a level of 0.001 to 10 percent; preferably 0.002 to 0.5 percent and more preferably 0.005 to 0.03 percent hydrogen peroxide, and contacting a bleachable substance with the admixture. Since ammonia is considered essential for successful bleaching of human hair, this composition is also advantageous for that purpose. Furthermore, since the ammonium hydroxide is produced in situ, contamination of the air with ammonia fumes is minimized.
  • a soluble ammonium salt is added to concentrated hydrogen peroxide containing 0.001 to 0.075, preferably 0.005 to 0.075, percent by weight of a soluble stannate salt (usually Na SnO '3H,O), which acts as a stabilizer for the naturally acidic hydrogen peroxide and also containing 0.001 to 0.5, preferably 0.0] to 0.3 percent by weight of an organic acid such as an alkylidene diphosphonic acid such as is known by the trade name of Dequest 2010, manufactured by Monsanto Chemical Company.
  • a soluble ammonium salt usually Na SnO '3H,O
  • Suitable alkylidene diphosphonic acids are of the formula Where X is hydrogen or the hydroxyl radical and n is a whole number from 0 to 5. These acids are further described in copending application Ser. No. 49,946, filed June 25, 1970, the disclosure of which is incorporated herein by reference. Although the mechanism is not well understood, the diphosphonic acid is thought to act as a sequestrant and form a complex with the tin salt, thereby preventing the precipitation of the latter by the NH, ions.
  • Other useful sequestrants include ethylenediaminetetracetic acid (EDTA), diethylenetriaminepentacetic acid (DTPA) and nitrilo trimethylene phosphonic acid (Dequest 2000").
  • Dequest 2 010 is preferred since it is exceptionally resistant to oxidation in H 0, solution in the presence of high concentrations of cations.
  • the pH of such a hydrogen peroxide solution will be about 2.0 to 3.0 but, if desired, may be adjusted within the range of about 0.5 to 7.0 by the addition of common acidifying or alkalining agents such as phosphonic acid or caustic soda.
  • the hydrogen peroxide will usually be prepared as about 35 percent by weight, although concentrations of percent or more, or as low as l percent, may also be used without detracting from the effectiveness of the invention.
  • the composition may also contain a soluble nitrate salt (e.g., sodium or ammonium nitrate) in a concentration of 0 to 0.50, preferably 0.001 to 0.07, percent.
  • a soluble nitrate salt e.g., sodium or ammonium nitrate
  • Such salts inhibit chloride corrosion of aluminum containers usually used to transport hydrogen peroxide.
  • Suitable stannate salts include sodium stannate trihydrate, sodium metastannate and potassium stannate. The composition thus formed has excellent stability.
  • the NH, ion may be provided by any of numerous salts, such as ammonium sulfate, nitrate, acetate, chloride, citrate, phosphate, and formate.
  • the ammonium salt may be added as crystals to the hydrogen peroxide solution, with stirring so as to effect dissolution.
  • the salt will be dissolved in an appropriate quantity of water and added to the hydrogen peroxide as a solution.
  • the bleaching composition may also advantageously contain any of various other chemicals whose uses are very familiar to the hydrogen peroxide art.
  • Such chemicals include, for instance, sulfates (e.g., magnesium sulfate) and phosphates.
  • ammonium hydroxide is known to be an activator, presumably of the free amide type, for the bleaching action of hydrogen peroxide.
  • the bleaching composition of this invention is made alkaline, as is done in almost all bleaching applications, the NH., which functions as a stable latent hydrogen peroxide activator, is converted to ammonium hydroxide.
  • the bleaching composition is quite stable in its acidic form, i.e., below about pH 7.0, when made alkaline, preferably about pH 9.0 to 11.0, the hydrogen peroxide is an active oxygen bleach whose effectiveness is significantly enhanced by the presence of the ammonium hydroxide.
  • the composition can be made alkaline by any of the various common alkalining agents, such as soluble silicates and phosphates (e.g., the alkali phosphates), soda ash, bo-
  • rax and caustic soda.
  • these chemicals are usually present in common household laundry detergents. ln ordinary usage, for instance, in home laundering, the concentrated bleaching composition will be considerably diluted. For home usage the bleaching composition may be diluted to a hydrogen peroxide level of about 3 to 6 percent for sale to the consumer. An appropriate quantity of this would be added to the detergent cycle of the washing machine to produce preferably 20 to 100 ppm oxygen. The alkalinity available from the detergent composition being used would convert the NH, present to ammonium hydroxide.
  • the bleaching composition has only a minor effect on the pH and total alkalinity of the common household detergents. Obviously, the bleaching composition may be utilized in more or less concentrated form, depending upon the usage, and separate alkalining agents may also be employed, if desired.
  • the ratio of NH, to H,O is not critical, however, a 0.8 to 1.021 ratio is desirable.
  • a 0.8 to 1.021 ratio is desirable.
  • approximately 30 percent ammonium salt would be recommended.
  • the beneficial effect in the dilute alkaline wash solution would be proportionally reduced.
  • a significantly high ratio would be precluded by the solubility of the ammonium salt in the 35% H,O,.
  • Temperature is not critical to the effectiveness of the bleaching composition; it may be employed in a socalled "cold wash as well as the normal hot wash. Useful temperatures cover the range of at least 50 to The invention is further illustrated by the following examples. Percentages are by weight.
  • EXAMPLE 1 To a commercial grade of hydrogen peroxide containing 35% H,O,, 0.1 percent Dequest 2010" and 0.01 percent sodium stannate was added, with stirring, 30 percent by weight of ammonium sulfate (NH,),SO, the balance being water. When solution was complete the pH of the resulting solution was adjusted to 2.0 with nitric acid.
  • NH, ammonium sulfate
  • EXAMPLE 3 A solution was made up as described in Example 1 except that ammonium nitrate was used instead of ammonium sulfate. This solution was then diluted to 3% H,O and tested as in Example 2. The active oxygen loss in 24 hours at C. was 3.3%, which is commercially satisfactory stability for the diluted product.
  • EXAMPLE 4 A solution was prepared, according to the procedure of Example 1, to have the following composition: 28% H,O,, 0.1 percent Dequest 2010, 20% (NH,),SO, the balance being water. The pH was 2.3 initially; this was adjusted to 0.5 by addition of nitric acid.
  • EXAMPLE 6 Two samples of standard (EMPA) stained cloth (blood, milk and Japanese ink; original brightness of 10 Hunter units) were washed for 100 minutes at F. in a Launder-O-Meter, the wash solution containing 0.15 percent Tide" detergent plus 75 ppm Alkalase enzyme, and 30 ppm active oxygen as hydrogen peroxide.
  • the control cloth washed with no NH ions in the solution, showed an increase in Hunter brightness of 6.9 units.
  • a stable aqueous bleaching composition having a pH of about 0.5 to 7.0 and, based on the total weight of the composition, consisting essentially of: (1) about 1 to about 50 weight percent hydrogen peroxide; (2) about 1 to about 50 weight percent of a water soluble ammonium salt; (3) about 0.001 to 0.075 weight percent of a soluble stannate salt selected from the group (SEX Hah-H 011 wherein X is hydrogen or the hydroxyl radical and n is a whole number from 0 to 5.
  • ammonium salt is selected from the group consisting of ammonium sulfate, nitrate, acetate, chloride, citrate, phosphate, and formate,
  • a composition of claim 1 containing approximately 25 to 50 percent hydrogen peroxide, 25 to 50 percent ammonium salt, 0.005 to 0.075 percent soluble stannate salt, 0.01 to 0.3 percent organic acid, and 0.001 to 0.07 percent soluble nitrate salt.
  • composition of claim 1 wherein the organic acid is an alkylidene diphosphonic acid.
  • a process for bleaching comprising admixing (a) an aqueous bleaching composition having a pH of about 0.5 to 7.0 with (b) an alkalining agent selected from the group consisting of soluble phosphates, silicates, soda ash, borax and caustic soda to make the pH of the resulting admixture approximately 9 to 1 l, diluting the admixture to a level of 0.002 to 0.5 weight percent hydrogen peroxide, and contacting a substance which is capable of being bleached by hydrogen peroxide with the admixture, said aqueous bleaching composition, based on the total weight of the composition, consisting essentially of 1) about 1 to about 50 weight percent hydrogen peroxide; (2) about 1 to about 50 weight percent of a water soluble ammonium salt; (3) about 0.001 to about 0.075 weight percent of asoluble stannate salt selected from the group consisting of sodium stannate trihydrate, sodium metastannate, and potassium stannate; and (4) about 0.01 to
  • a process for bleaching comprising admixing a composition of claim 1 with an alkalining agent in such quantity as to make the pH of the resulting admixture greater than 7.0, diluting the admixture to a level of 0.001 to 10 percent, and contacting a substance which is capable of being bleached by hydrogen peroxide with the admixture.
  • alkalining agent is selected from the group consisting of soluble phosphates, silicates, soda ash, borax, and caustic soda.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
US00268051A 1972-06-30 1972-06-30 Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith Expired - Lifetime US3811833A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00268051A US3811833A (en) 1972-06-30 1972-06-30 Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith
CA173,982A CA1003605A (en) 1972-06-30 1973-06-13 Stabilized hydrogen peroxide compositions containing ammonium ions, and process for bleaching therewith
IT26029/73A IT990818B (it) 1972-06-30 1973-06-28 Composizioni di perossido di idrogeno stabilizzato contenenti ioni ammonio e processo di sbian ca con tali composizioni
BE132921A BE801681A (fr) 1972-06-30 1973-06-29 Compositions stabilisees a base d'eau oxygenee contenant des ions ammonium et procede de blanchiment les utilisant
FR7323905A FR2190912B1 (enrdf_load_stackoverflow) 1972-06-30 1973-06-29
DE19732333201 DE2333201A1 (de) 1972-06-30 1973-06-29 Bleichverfahren und -mittel
JP48073343A JPS4952784A (enrdf_load_stackoverflow) 1972-06-30 1973-06-30
GB3149373A GB1419184A (en) 1972-06-30 1973-07-02 Bleaching composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00268051A US3811833A (en) 1972-06-30 1972-06-30 Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith

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US3811833A true US3811833A (en) 1974-05-21

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US00268051A Expired - Lifetime US3811833A (en) 1972-06-30 1972-06-30 Stabilized hydrogen peroxide compositions containing ammonium ions,and process for bleaching therewith

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US (1) US3811833A (enrdf_load_stackoverflow)
JP (1) JPS4952784A (enrdf_load_stackoverflow)
BE (1) BE801681A (enrdf_load_stackoverflow)
CA (1) CA1003605A (enrdf_load_stackoverflow)
DE (1) DE2333201A1 (enrdf_load_stackoverflow)
FR (1) FR2190912B1 (enrdf_load_stackoverflow)
GB (1) GB1419184A (enrdf_load_stackoverflow)
IT (1) IT990818B (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996151A (en) * 1975-02-18 1976-12-07 Basf Aktiengesellschaft Alkaline peroxide bleach liquor
US4238192A (en) * 1979-01-22 1980-12-09 S. C. Johnson & Son, Inc. Hydrogen peroxide bleach composition
DE3112854A1 (de) * 1980-04-01 1982-01-07 Interox Chemicals Ltd., London "fluessiges bleichmittel"
US4362639A (en) * 1981-04-03 1982-12-07 Warner-Lambert Company Cleanser with improved afterodor and tarnish resistance
US4378967A (en) * 1979-01-26 1983-04-05 Mitsubishi Gas Chemical Co., Inc. Process for bleaching fibrous material by hydrogen peroxide
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US5006124A (en) * 1989-12-15 1991-04-09 Fmc Corporation Wet processing of denim
WO1992017634A1 (en) * 1991-03-28 1992-10-15 Interface, Inc. Method for removing stains from carpet and textiles
US5348556A (en) * 1988-06-14 1994-09-20 Basf Corporation Volatile carpet sanitizing shampoo containing hydrogen peroxide
US5736497A (en) * 1995-05-05 1998-04-07 Degussa Corporation Phosphorus free stabilized alkaline peroxygen solutions
US5814304A (en) * 1996-08-02 1998-09-29 Colgate Palmolive Company Stable aqueous abrasive peroxide tooth whitening dentifrice
US20040244871A1 (en) * 2003-06-04 2004-12-09 Min-Ju Chung Method for forming a colored red oak product
EP3427719B1 (en) * 2017-07-14 2024-03-06 Kao Germany GmbH Aqueous bleaching and dyeing composition for keratin fibers, process, kit and use thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60212500A (ja) * 1984-04-06 1985-10-24 三井東圧化学株式会社 過酸化水素漂白方法およびそれに用いる漂白剤組成物
JPS6160799A (ja) * 1984-08-31 1986-03-28 株式会社東芝 洗浄液
TR24867A (tr) * 1989-08-23 1992-07-01 Unilever Nv CAMASIR MUAMELE MAMULü
JP2602563B2 (ja) * 1989-12-15 1997-04-23 花王株式会社 液体酸素系漂白剤組成物
IN176964B (enrdf_load_stackoverflow) * 1992-11-27 1996-10-12 Lever Hindustan Ltd

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3687627A (en) * 1970-06-25 1972-08-29 Du Pont Stabilized hydrogen peroxide solutions

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996151A (en) * 1975-02-18 1976-12-07 Basf Aktiengesellschaft Alkaline peroxide bleach liquor
US4238192A (en) * 1979-01-22 1980-12-09 S. C. Johnson & Son, Inc. Hydrogen peroxide bleach composition
US4378967A (en) * 1979-01-26 1983-04-05 Mitsubishi Gas Chemical Co., Inc. Process for bleaching fibrous material by hydrogen peroxide
DE3112854A1 (de) * 1980-04-01 1982-01-07 Interox Chemicals Ltd., London "fluessiges bleichmittel"
US4362639A (en) * 1981-04-03 1982-12-07 Warner-Lambert Company Cleanser with improved afterodor and tarnish resistance
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US5348556A (en) * 1988-06-14 1994-09-20 Basf Corporation Volatile carpet sanitizing shampoo containing hydrogen peroxide
JPH0723579B2 (ja) 1989-12-15 1995-03-15 エフ エム シー コーポレーション デニムの湿式加工
US5006124A (en) * 1989-12-15 1991-04-09 Fmc Corporation Wet processing of denim
WO1991009171A1 (en) * 1989-12-15 1991-06-27 Fmc Corporation Wet processing of denim
US5259848A (en) * 1990-06-11 1993-11-09 Interface, Inc. Method for removing stains from carpet and textiles
WO1992017634A1 (en) * 1991-03-28 1992-10-15 Interface, Inc. Method for removing stains from carpet and textiles
US5736497A (en) * 1995-05-05 1998-04-07 Degussa Corporation Phosphorus free stabilized alkaline peroxygen solutions
US5814304A (en) * 1996-08-02 1998-09-29 Colgate Palmolive Company Stable aqueous abrasive peroxide tooth whitening dentifrice
US20040244871A1 (en) * 2003-06-04 2004-12-09 Min-Ju Chung Method for forming a colored red oak product
EP3427719B1 (en) * 2017-07-14 2024-03-06 Kao Germany GmbH Aqueous bleaching and dyeing composition for keratin fibers, process, kit and use thereof

Also Published As

Publication number Publication date
BE801681A (fr) 1973-10-15
DE2333201A1 (de) 1974-01-24
JPS4952784A (enrdf_load_stackoverflow) 1974-05-22
GB1419184A (en) 1975-12-24
FR2190912A1 (enrdf_load_stackoverflow) 1974-02-01
FR2190912B1 (enrdf_load_stackoverflow) 1977-02-18
CA1003605A (en) 1977-01-18
IT990818B (it) 1975-07-10

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