US3167513A - Bleaching compositions - Google Patents

Bleaching compositions Download PDF

Info

Publication number
US3167513A
US3167513A US797053A US79705359A US3167513A US 3167513 A US3167513 A US 3167513A US 797053 A US797053 A US 797053A US 79705359 A US79705359 A US 79705359A US 3167513 A US3167513 A US 3167513A
Authority
US
United States
Prior art keywords
per
acid
bleaching
urea
acids
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
US797053A
Other languages
English (en)
Inventor
Jan Cirksena Meerkamp V Embden
Boldingh Jan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lever Brothers Co
Original Assignee
Lever Brothers Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lever Brothers Co filed Critical Lever Brothers Co
Application granted granted Critical
Publication of US3167513A publication Critical patent/US3167513A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/3945—Organic per-compounds

Definitions

  • bleaching compositions especially detergent bleaching compositions, contain inorganic per-compounds such as sodium perborate or percarbonate. These percompounds provide a satisfactory bleach when the composition is used at the boil, but at lower temperatures their action is too slow to be really effective within the normal bleaching time. Moreover, the amount of oxygen used actually in bleaching is rather low in comparison with the total amount of available oxygen.
  • bleaching compositions containing an organic per-carboxylic acid such as for example peracetic acid. Owing to the instability of such compounds, particularly in alkaline conditions such as occur normally in detergent compositions, it has, however, been necessary to prepare them only shortly before use. On account of this, it has not been possible to use them commercially, since bleaching compositions are generally used some time after manufacture, especially when they are intended for use in the home.
  • organic per-carboxylic acids derived from monoor di-carboxylic acids, and their derivatives such as the acyl peroxides, can be made into excellent stable bleaching compositions by combining them with urea to form adducts or so-called inclusion compounds.
  • urea forms inclusion compounds with various organic compounds, such as aliphatic hydrocarbons, alcohols, aldehydes, ketones and acids. It was, however not known that urea also exhibits this property with organic per-carboxylic acids and acyl V peroxides.
  • the organic perin inclusion compounds with urea become stabilised to such an extent that they can be used a long time after their preparation.
  • the per-acids and acyl peroxides derived from dicarboxylic acids are not affected by other ingredients normally used in bleaching and detergent compositions.
  • the present invention therefore, provides an inclusion compound of urea and a per-derivative of a straight-chain aliphatic carboxylic acid.
  • Inclusion compounds in accordance with the present invention may be formed by organic alpha-monopercarboxylic acids containing at least 4 carbon atoms in the molecule and by organic per-alpha: omega-dicarboxylic acids containing at least carbon atoms in the molecule.
  • Per-acids containing up to 20 carbon atoms in the molecule may be used; per-monocarboxylic acids containing from 6 to 10 carbon atoms and per-dicarboxylic acids containing from 10 to 14 carbon atoms are preferred.
  • Per-acids of this type may be derived from saturated aliphatic monoor dicarboxylic acids and include, for instance per-butyric acid, per-valeric acid, per caproic acid, per-heptanoic acid, per-caprylic acid, perpelargonic acid, per-capric acid, per-undecanoic acid, per-lauric acid, per-myristic acid, per-palmitic acid, perstearic acid, monoand di-per-sebacic acids and monoand di-per-brassylic acids.
  • Per-acids containing substituents such as, for example, methyl, hydroxy, or keto groups and those containing double bonds may also be used.
  • Inclusion compounds according to the invention may also be formed by acyl peroxides derived from aliphatic monoor dicarboxylic acids, in particular from the acids quoted above. In mixed acyl peroxides, however, one of the groups may be derived from an aliphatic monoor dicarboxylic acid having a shorter carbon chain than these acids.
  • the acyl peroxides have the general formulae:
  • R and R are aliphatic hydrocarbon groups containing from 1 to 19 carbon atoms in a straight chain and R" is a divalent hydrocarbon group containing from 1 to 18 carbon atoms in a straight chain, with the restriction that either R or R contains at least 3 carbon atoms in a straight chain or R" contains at least 8 carbon atoms in a straight chain.
  • R, R, and R may each be substituted and may contain the same or different numbers of carbon atoms.
  • the method of preparation of the per-acids and acyl peroxides is not a feature of the invention. Two useful methods of preparing the per-acids are illustrated, however, in the examples, while the acyl peroxides may, for example, be prepared by the reaction of a per-acid with an acid illustrated by the following equation:
  • acyl peroxides are often formed in subsidiary amounts in the preparation of the per-acids.
  • the inclusion compounds according to the invention may be prepared by treating the per-derivatives with urea in any known way for preparing inclusion compounds, for example by mixing them with the urea dissolved in a solvent such as methanol and isolating the product by crystallisation or evaporation.
  • a solvent such as methanol
  • the products so obtained are crystalline substances having the usual structure of inclusion compounds of urea.
  • All the products of the invention are very stable, but particularly stable products are obtained if a smallamount of sulphuric acid, preferably (LS-3% by weight of the per-derivative, is added during the preparation of the inclusion compound. They do not explode or ignite when heated or subjected to shock and they do not lose oxygen to any appreciable extent when kept at room temperature. They may frequently be mixed with other substances without losing their stability. Their stability is, however, diminished by the presence of alkaline compounds. This diminution is less with per-derivatives of dicarboxylic acids than with per-derivatives of monocarboxylic acids and, in particular, the inclusion compounds derived from per-derivatives of di-carboxylic acids are very stable in the presence of the usual ingredients of detergent compositions.
  • a smallamount of sulphuric acid preferably (LS-3% by weight of the per-derivative
  • the products of the invention are, moreover, strongly bactericidal, for example against Escherichia coli and Staphylococcus aureus. 3
  • soap or organic soapless detergents such as, for example, alkylaryl sulphonates, alkyl sulphates, fatty monoglyceride sulphates, salts of amides of taurine or methyltaurine, and salts of esters or ethers of isethionic acid. They may also contain alkali-metal carbonates, silicates, sulphates, and phosphates, such as orthophosphates, pyrophosphates, polyphosphates and metaphosphates, and other conventional ingredients of detergent compositions such as carboxy-methylcellulose, lather improvcrs, fluorescent brightening agents, anti-tarnishing agents, perfumes and the like. Inorganic per-compounds such as perborates and percarbonates may also be present. They may be in any solid form, such as powders, chips, flakes, bars or tablets.
  • the amount of inclusion compound to be incorporated in a bleaching composition depends on various factors such as the bleaching effect required and the nature and concentration of the per-acid in the inclusion compound.
  • Bleaching compositions have been found particularly useful in which the amount of inclusion compound corresponds to from 0.05 to preferably from 0.3 to 1.5%, by weight of the total composition, of active oxygen.
  • EXAMPLE 1 (a) 50 g. (0.8 mol) of boric acid were mixed with 250 g. (2.45 mols) of acetic acid anhydride and heated to 90 C. During the reaction the temperature increased to 120 C. owing to the heat of reaction evolved. On cooling the reaction mixture, pyroboric acetate was obtained in a yield of 92% calculated on the amount of boric acid used.
  • the mixture was then cooled to -10 C. and the contaminated urea which precipitated was filtered oil.
  • filtrate was freed from methanol by evaporation at 40 C. under a vacuum of 15 mm. Hg.
  • the residue (29.5 g.) consisted mainly of the urea inclusion compounds or percaprylic acid and dicapryl peroxide. It contained about 18% by weight of the per-compounds. It was very stable; on keeping some at room temperature for 7 days no loss of active oxygen could be detected.
  • EXAMPLE 2 (a) To 39.8 g. (0.2 mol) of lauric acid dissolved in 61.2 g. (0.6 mol) of sulphuric acid (96%) were gradually added 20.5 g. (0.3 mol) of a 50% hydrogen peroxide solution at 10 C. with constant stirring. After the addition, stirring was continued for 3 hours at 15 C. The suspension thus obtained was diluted with ice-water, which caused the per-acid to precipitate. The precipitate was filtered off, Washed four times with ice-water and dried in a vacuum desiccator. 39.1 g. of dry crystalline product containing 89% of per-lauric acid were obtained (yield 81%).
  • EXAMPLE 3 (a) To 20.2 g. (0.1 mole) of sebacic acid dissolved in 140 g. (1.2 moles) of sulphuric acid (85%) were gradually added 34 g. (0.3 mol) of a 30% hydrogen peroxide solution at 10 C. with constant stirring. After the addition, stirring was continued for 2 hours at 20 C. The per-acid precipitated in small crystals and was filtered off, washed four times with ice-water and dried in a vacuum desiccator. 21.5 g. of di-persebacic acid of 96% purity were obtained (yield 88%).
  • EXAMPLE 4 (a) To 23.4 g. (0.096 mol) of brassylic acid dissolved in 140 g. (1.2 moles) of sulphuric acid (85%) were gradually added 20.4 g. (0.3 mol) of a 50% hydrogen peroxide solution at 10-15 C. with constant stirring. After the addition, stirring was continued for 6 hours at 20 C. The per-acid precipitated in small crystals and was filtered off, washed four times with ice-water and dried in a vacuum desiccator.
  • Pieces of cotton stained with tea were washed in these solutions at different temperatures and for different times.
  • the cotton to washing liquid ratio was 1:20.
  • the table below shows the results, expressed as increase in percent reflection measured with an Elrepho reflectometer.
  • a bleaching composition which contains an inclusion compound of urea and a per-derivative of a straightchain aliphatic alpha-monocarboxylic acid containing 4 to 20 carbon atoms in an amount sufiicient to impart eifective bleaching properties to the composition.
  • a bleaching composition which contains an inclusion compound of urea and per-caprylic acid in an amount sufficient to impart effective bleaching properties to the composition.
  • a bleaching composition which contains an inclusion compound of urea and per-lauric acid in an amount sufficient to impart effective bleaching properties to the composition.
  • a bleaching composition which contains an inclusion compound of urea and a per-derivative of a straightchain aliphatic alpha:omega-dicarboxylic acid containing 10 to 20 carbon atoms in an amount sufficient to impart effective bleaching properties to the composition.
  • a bleaching composition which contains an inclusion compound of urea and di-per-sebacic acid in an amount sufiicient to impart effective bleaching properties to the composition.
  • a bleaching composition which contains an inclusion compound of urea and di-per-brassylic acid in an amount sufficient to impart effective bleaching properties to the composition.
  • a bleaching composition which contains as a bleaching agent an inclusion compound of urea and di-perbrassylic acid in an amount corresponding to 0.05-10%, by weight of the total composition, of active oxygen.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US797053A 1958-03-07 1959-03-04 Bleaching compositions Expired - Lifetime US3167513A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7391/58A GB847702A (en) 1958-03-07 1958-03-07 Improvements in or relating to bleaching compositions

Publications (1)

Publication Number Publication Date
US3167513A true US3167513A (en) 1965-01-26

Family

ID=9832235

Family Applications (1)

Application Number Title Priority Date Filing Date
US797053A Expired - Lifetime US3167513A (en) 1958-03-07 1959-03-04 Bleaching compositions

Country Status (8)

Country Link
US (1) US3167513A (enrdf_load_stackoverflow)
BE (1) BE576395A (enrdf_load_stackoverflow)
CH (2) CH363019A (enrdf_load_stackoverflow)
DE (2) DE1297572B (enrdf_load_stackoverflow)
ES (1) ES248199A1 (enrdf_load_stackoverflow)
FR (1) FR1221993A (enrdf_load_stackoverflow)
GB (1) GB847702A (enrdf_load_stackoverflow)
NL (3) NL110936C (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977988A (en) * 1974-03-23 1976-08-31 Kao Soap Co., Ltd. Stabilized sodium percarbonate and process for preparing same
US4181621A (en) * 1975-07-08 1980-01-01 Blendax-Werke R. Schneider & Co. Cleaning agents for dentures
US4374035A (en) * 1981-07-13 1983-02-15 The Procter & Gamble Company Accelerated release laundry bleach product
US4391724A (en) * 1981-10-21 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
US4391723A (en) * 1981-07-13 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
US4391725A (en) * 1981-10-21 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
EP0103416A1 (en) * 1982-08-19 1984-03-21 THE PROCTER & GAMBLE COMPANY Peroxyacid bleach compositions
WO1996012003A1 (en) * 1994-10-13 1996-04-25 Fmc Corporation Stable peracid sols, gels and solids and a process therefor
EP1811014A1 (en) 2006-01-23 2007-07-25 The Procter and Gamble Company A composition comprising a pre-formed peroxyacid and a bleach catalyst
WO2007138491A1 (en) * 2006-05-26 2007-12-06 The Procter & Gamble Company Detergent and bleach compositions

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013581A (en) * 1975-07-10 1977-03-22 The Procter & Gamble Company Bleach tablet composition
DE3276581D1 (en) * 1981-08-31 1987-07-23 Procter & Gamble Laundry bleach product
GB9120958D0 (en) * 1991-10-02 1991-11-13 Procter & Gamble Bleaching composition

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1628015A (en) * 1923-05-08 1927-05-10 Frank A Bower Washing compound
US1718609A (en) * 1929-06-25 Amd vaman r
US2141189A (en) * 1933-12-22 1938-12-27 Henkel & Cie Gmbh Bleaching and cleansing compositions
US2143060A (en) * 1934-02-23 1939-01-10 Max Goldmann Solid, sticklike shaving preparation
US2202478A (en) * 1938-12-01 1940-05-28 Du Pont Bleaching of cotton
US2259479A (en) * 1938-08-03 1941-10-21 Sales Affiliates Inc Process for the manufacture of the solid compound of hydrogen peroxide and urea
US2362401A (en) * 1944-11-07 Detergent compositions
US2430450A (en) * 1945-02-20 1947-11-11 Brown Ethan Allan Antiseptic urea peroxide-glycerol solution
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2527640A (en) * 1947-05-15 1950-10-31 Hercules Powder Co Ltd Stabilization of hydroperoxides
US2535313A (en) * 1946-02-18 1950-12-26 Gen Foods Corp Preparation of flour bleaching compositions
US2596344A (en) * 1948-08-21 1952-05-13 Shell Dev Fractionation process
US2598953A (en) * 1952-06-03 Separation of orgsnic issuers
US2675356A (en) * 1950-10-23 1954-04-13 Du Pont Detergent compositions
US2727025A (en) * 1951-11-16 1955-12-13 Standard Oil Co Urea adducts of polyol esters
US2750362A (en) * 1952-12-05 1956-06-12 Swern Daniel Peroxides of long-chain olefinc compounds
US2830039A (en) * 1953-08-31 1958-04-08 Standard Oil Co Urea adducts of quaternary heterocyclic-nitrogen halides
US2899965A (en) * 1959-08-18 Bromate-urea oxidative fixing

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2598953A (en) * 1952-06-03 Separation of orgsnic issuers
US1718609A (en) * 1929-06-25 Amd vaman r
US2362401A (en) * 1944-11-07 Detergent compositions
US2899965A (en) * 1959-08-18 Bromate-urea oxidative fixing
US1628015A (en) * 1923-05-08 1927-05-10 Frank A Bower Washing compound
US2141189A (en) * 1933-12-22 1938-12-27 Henkel & Cie Gmbh Bleaching and cleansing compositions
US2143060A (en) * 1934-02-23 1939-01-10 Max Goldmann Solid, sticklike shaving preparation
US2259479A (en) * 1938-08-03 1941-10-21 Sales Affiliates Inc Process for the manufacture of the solid compound of hydrogen peroxide and urea
US2202478A (en) * 1938-12-01 1940-05-28 Du Pont Bleaching of cotton
US2498344A (en) * 1944-12-23 1950-02-21 Lever Brothers Ltd Denture cleansers
US2430450A (en) * 1945-02-20 1947-11-11 Brown Ethan Allan Antiseptic urea peroxide-glycerol solution
US2535313A (en) * 1946-02-18 1950-12-26 Gen Foods Corp Preparation of flour bleaching compositions
US2527640A (en) * 1947-05-15 1950-10-31 Hercules Powder Co Ltd Stabilization of hydroperoxides
US2596344A (en) * 1948-08-21 1952-05-13 Shell Dev Fractionation process
US2675356A (en) * 1950-10-23 1954-04-13 Du Pont Detergent compositions
US2727025A (en) * 1951-11-16 1955-12-13 Standard Oil Co Urea adducts of polyol esters
US2750362A (en) * 1952-12-05 1956-06-12 Swern Daniel Peroxides of long-chain olefinc compounds
US2830039A (en) * 1953-08-31 1958-04-08 Standard Oil Co Urea adducts of quaternary heterocyclic-nitrogen halides

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977988A (en) * 1974-03-23 1976-08-31 Kao Soap Co., Ltd. Stabilized sodium percarbonate and process for preparing same
US4181621A (en) * 1975-07-08 1980-01-01 Blendax-Werke R. Schneider & Co. Cleaning agents for dentures
US4374035A (en) * 1981-07-13 1983-02-15 The Procter & Gamble Company Accelerated release laundry bleach product
US4391723A (en) * 1981-07-13 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
US4391724A (en) * 1981-10-21 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
US4391725A (en) * 1981-10-21 1983-07-05 The Procter & Gamble Company Controlled release laundry bleach product
EP0103416A1 (en) * 1982-08-19 1984-03-21 THE PROCTER & GAMBLE COMPANY Peroxyacid bleach compositions
US4529534A (en) * 1982-08-19 1985-07-16 The Procter & Gamble Company Peroxyacid bleach compositions
WO1996012003A1 (en) * 1994-10-13 1996-04-25 Fmc Corporation Stable peracid sols, gels and solids and a process therefor
US5597791A (en) * 1994-10-13 1997-01-28 Fmc Corporation Stable peracid sols, gels and solids
EP1811014A1 (en) 2006-01-23 2007-07-25 The Procter and Gamble Company A composition comprising a pre-formed peroxyacid and a bleach catalyst
WO2007083276A1 (en) * 2006-01-23 2007-07-26 The Procter & Gamble Company A composition comprising a pre-formed peroxyacid and a bleach catalyst
US20070173428A1 (en) * 2006-01-23 2007-07-26 The Procter & Gamble Company Composition comprising a pre-formed peroxyacid and a bleach catalyst
WO2007138491A1 (en) * 2006-05-26 2007-12-06 The Procter & Gamble Company Detergent and bleach compositions

Also Published As

Publication number Publication date
CH363019A (de) 1962-07-15
NL236860A (enrdf_load_stackoverflow)
NL110936C (enrdf_load_stackoverflow)
FR1221993A (fr) 1960-06-07
DE1297572B (de) 1969-06-19
CH378869A (de) 1964-06-30
ES248199A1 (es) 1959-10-16
BE576395A (enrdf_load_stackoverflow)
DE1290648B (de) 1969-03-13
GB847702A (en) 1960-09-14
NL110937C (enrdf_load_stackoverflow)

Similar Documents

Publication Publication Date Title
US3167513A (en) Bleaching compositions
US4100095A (en) Peroxyacid bleach composition having improved exotherm control
US3686127A (en) Detergent bleach
CA1234326A (en) Bodies containing stabilized bleach activators
US4259201A (en) Detergent composition containing organic peracids buffered for optimum performance
US5520844A (en) Imide-aromatic peroxyacids as bleaching agents
US3177148A (en) Bleaching processes and compositions
US5069812A (en) Bleach/builder precursors
US5114611A (en) Bleach activation
EP0122763B1 (en) Bleach compositions
EP0103416B1 (en) Peroxyacid bleach compositions
EP0267175B1 (en) Sulfone peroxycarboxylic acids
US3075921A (en) Substituted peroxybenzoic acid bleaching agents
US4824591A (en) Sulfone peroxycarboxylic acids
US4119660A (en) Method for making diperoxyacids
US3816324A (en) Bleaching compositions containing a n-acyl azole
US4758369A (en) Sulfone peroxycarboxylic acids
JPS6017786B2 (ja) アシルペルオキシド、漂白組成物および漂白法
US4221675A (en) Percompound activators
US5089166A (en) Bleaching and detergent compositions
EP0426217A2 (en) Bleach precursors
US5380456A (en) Stabilization of aqueous persalt solutions
US2362401A (en) Detergent compositions
NO131069B (enrdf_load_stackoverflow)
US4487723A (en) Substituted-butanediperoxoic acids and process for bleaching