US3167513A - Bleaching compositions - Google Patents
Bleaching compositions Download PDFInfo
- 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
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)
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 (xx) |
BE (1) | BE576395A (xx) |
CH (2) | CH378869A (xx) |
DE (2) | DE1297572B (xx) |
ES (1) | ES248199A1 (xx) |
FR (1) | FR1221993A (xx) |
GB (1) | GB847702A (xx) |
NL (3) | NL110937C (xx) |
Cited By (10)
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 |
US4391725A (en) * | 1981-10-21 | 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 |
US4391723A (en) * | 1981-07-13 | 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)
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)
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 |
-
0
- NL NL110936D patent/NL110936C/xx active
- BE BE576395D patent/BE576395A/xx unknown
- NL NL236860D patent/NL236860A/xx unknown
- NL NL110937D patent/NL110937C/xx active
-
1958
- 1958-03-07 GB GB7391/58A patent/GB847702A/en not_active Expired
-
1959
- 1959-03-04 US US797053A patent/US3167513A/en not_active Expired - Lifetime
- 1959-03-06 ES ES0248199A patent/ES248199A1/es not_active Expired
- 1959-03-06 DE DEU6043A patent/DE1297572B/de active Pending
- 1959-03-06 DE DEU8003A patent/DE1290648B/de active Pending
- 1959-03-07 FR FR788710A patent/FR1221993A/fr not_active Expired
- 1959-03-07 CH CH7048759A patent/CH378869A/de unknown
- 1959-03-07 CH CH7048859A patent/CH363019A/de unknown
Patent Citations (18)
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)
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 |
US4391725A (en) * | 1981-10-21 | 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 |
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 |
---|---|
FR1221993A (fr) | 1960-06-07 |
NL110936C (xx) | |
DE1297572B (de) | 1969-06-19 |
CH363019A (de) | 1962-07-15 |
GB847702A (en) | 1960-09-14 |
NL236860A (xx) | |
BE576395A (xx) | |
DE1290648B (de) | 1969-03-13 |
CH378869A (de) | 1964-06-30 |
ES248199A1 (es) | 1959-10-16 |
NL110937C (xx) |
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