US3562171A - Oxygen carrier for detergent compositions - Google Patents
Oxygen carrier for detergent compositions Download PDFInfo
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- US3562171A US3562171A US789003A US3562171DA US3562171A US 3562171 A US3562171 A US 3562171A US 789003 A US789003 A US 789003A US 3562171D A US3562171D A US 3562171DA US 3562171 A US3562171 A US 3562171A
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- US
- United States
- Prior art keywords
- substrate
- borax
- particle size
- peroxyhydrate
- carrier
- 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
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- 239000003599 detergent Substances 0.000 title abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 25
- 239000001301 oxygen Substances 0.000 title abstract description 25
- 239000000203 mixture Substances 0.000 title description 16
- 150000003839 salts Chemical class 0.000 abstract description 38
- 239000007787 solid Substances 0.000 abstract description 35
- 239000002245 particle Substances 0.000 abstract description 29
- 239000000758 substrate Substances 0.000 abstract description 29
- 229910021538 borax Inorganic materials 0.000 abstract description 15
- 239000004328 sodium tetraborate Substances 0.000 abstract description 15
- 235000010339 sodium tetraborate Nutrition 0.000 abstract description 15
- 239000002002 slurry Substances 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 21
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 19
- 239000008187 granular material Substances 0.000 description 18
- 239000007844 bleaching agent Substances 0.000 description 14
- 239000007859 condensation product Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 150000002191 fatty alcohols Chemical class 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- -1 alkyl phenols Chemical class 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003760 tallow Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229960001922 sodium perborate Drugs 0.000 description 6
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 6
- 238000005204 segregation Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000320 mechanical mixture Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940096386 coconut alcohol Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/005—Stabilisation of the solid compounds subsequent to the preparation or to the crystallisation, by additives or by coating
-
- 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
- C11D3/3942—Inorganic per-compounds
Definitions
- a fast dissolving, nonsegregating oxygen carrier for granular detergents consisting essentially of 4.5% to 59% finely divided peroxyhydrate salt imbedded in to 88% of a water-soluble waxy solid, said waxy solid adhering to 4.5% to of granular borax substrate, said substrate having a bulk density of 0.03 to 0.56 g./cc. and a particle size between 0.074 mm. and 3.36 mm.
- a process for preparing the oxygen carrier is also disclosed in which the waxy solid is dissolved in a volatile organic solvent, the peroxyhydrate salt is slurried into the solution, and the slurry is sprayed onto a falling curtain of the granular borax.
- This invention relates to a fast-dissolving, non-segregating oxygen bleach carrier designed for mixing with detergent granules, and the process for preparing said oxygen carrier.
- the peroxyhydrate salt contains hydrogen peroxide bleach within its crystal structure, and therefore serves as a carrier for incorporating active oxygen bleach into detergent compositions.
- Sodium perborate tetrahydrate is the most common peroxyhydrate salt used in these mixtures.
- An object of this invention is to formulate a fast-dissolving, oxygen bleach carrier which can be produced at a density and particle size which approximately match that of the detergent granule with which it is to be mixed.
- Another object of the invention is to provide an efficient process by which such an oxygen bleach carrier can be made.
- the objects of this invention can be accomplished by a process comprising the steps of (1) dissolving a watersoluble, waxy solid in a volatile solvent, (2) adding a finely divided peroxyhydrate salt to the solution to form a slurry and (3) spraying this slurry onto a granular borax substrate of a preselected bulk density and particle size (described hereinafter as puffed borax), said substrate being formed into a falling curtain to receive the spray-on.
- puffed borax a granular borax substrate of a preselected bulk density and particle size
- the volatile solvent evaporates, leaving behind a crisp, free flowing, fast dissolving granular composition, comprising a puffed borax substrate with finely divided crystalline peroxyhydrate salt imbedded in an outer coating of water-soluble, waxy solid adhering to said substrate.
- the puffed borax used in the present invention can 3,562,171 Patented Feb. 9, 1971 be produced by the process disclosed in an article by R. C. Rhees et al., Soap and Chemical Specialties. vol. XLll, January 1966. pages 58-61 and 118-120.
- This article describes how borax particles which normally have a bulk density of about 1 g./cc., can be made to puff by rapid heating, and thus be greatly reduced in bulk density.
- the puffed borax can be produced within a wide range of particle size and bulk density, Densities between 0.03 and 0.56 g./cc. have been obtained.
- the puffed borax substrate must have a bulk density and particle size such that the resulting carrier has particle characteristics approximating those of the detergent granules with which it is to be mixed.
- Such detergent granules generally have a particle size within the range of 0.074 mm. to 3.36 mm. (through No. 6 and on No. 200U.S. Standard Sieve Series), and a bulk density of 0.2 to 0.8 g./cc.
- a nonsegregating oxygen bleach carrier must also have particle size and density which fall within these ranges.
- the detergent granules with which the oxygen bleach carrier is to be mixed will have a bulk density within the range specified above.
- the detergent will comprise granules which are not uniform in size, but which have a particle size distribution within the range mentioned above.
- the bulk density and particle size distribution of the puffed borax substrate should be chosen so that the resulting oxygen bleach carrier will have a bulk density and particle size distribution which match closely those of the detergent granules with which the carirer is mixed.
- due regard must be had to the increase in density which will occur as a result of the addition of organic solid and peroxyhydrate salt to the substrate.
- a puffed borax density less than that of the detergent granules will generally be chosen; precisely how much less depends on the amount of peroxyhydrate salt intended to be added to the substrate. For instance, see Example I below. where pufied borax of 0.2 g./cc. bulk density was used to obtain a carrier having a bulk density of 0.35 g./cc.
- the addition of peroxyhydrate salt to the puffed borax substrate has little effect on the particle size of the substrate, because the peroxyhydrate salt/waxy solid matrix primarily fills the voids in the irregular surface of the puffed borax granules. Therefore, the particle size distribution of the pulled borax chosen for use as a substrate should be approximately the same as that of the detergent granules with which the oxygen bleach carrier is mixed.
- the borax In addition to its function as a substrate in the oxygen bleach carrier of the present invention, the borax also serves a useful function as a pH buffer in the detergent composition to which the oxygen bleach carrier is added.
- the water-soluble, waxy solid used in the present invention to cause the peroxyhydrate salt to adhere to the memeied borax substrate can be selected from a wide range of such materials well known in the detergent art. The only requirement is that it be water-soluble and that it be a waxy solid at ambient temperatures (i.e.. at temperatures between 18 C. to 38 C.). Water solubility is necessary to facilitate rapid dissolving 0f the entire carrier composition, and the solid waxy physical state at ambient temperatures is necessary to keep the peroxyhydrate salt in adhesion to the puffed borax substrate, and at the same time keep the oxygen carrier in the form of a dry free flowing granule.
- water-soluble, waxy solids which are suitable for the purpose of this invention, but the more suitable ones are solid condensation products of a low molecular weight alkylene oxide and a hydrophobic moiety.
- Preferred water-soluble, waxy, solid condensation products are those of 650 moles of ethylene oxide with one mole of any of the following: (1) fatty alcohols of 22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 812 carbon atoms in the alkyl chain.
- these waxy materials form a coating around the peroxyhydrate salt thus reducing or preventing undesirable interactions between the peroxyhydrate salt and other ingredients (e.g., enzymes and free water) which may be present in the detergent granule.
- other ingredients e.g., enzymes and free water
- the above materials have been mentioned only as examples of water-soluble, Waxy solids which are particularly suitable for use in this invention, and there is no intention that the invention be limited to those mentioned. One skilled in the art could readily select many more such water-soluble, waxy solids which would be suitable.
- the peroxyhydrate salts used must have a particle size of less than 0.210 mm. (No. 70 U.S. Standard Sieve Series) in order to obtain the fast dissolving carrier of this invention, and greater than 0.044 mm. (No. 325 U.S. Standard Screen) in order to avoid excessive dust problems in handling.
- the particle size should be between 0.149 mm. (No. 100 U.S. Standard Sieve Series) and 0.063 mm. (No. 230 U.S. Standard Sieve Series).
- These salts can be selected from the group consisting of the peroxyhydrates of the alkali metal borates, carbonates, silicates and phosphates, particularly the sodium and potassium salts. These salts are called peroxyhydrates because they contain hydrogen peroxide in their crystalline structure. Well known examples from this group are the sodium perborate and sodium percarbonate commonly used in the detergent industry.
- the solvent used in this invention should have a boiling point within the range of about 55 C. to 110 C. so as to be in the liquid state and easily handled at the ambient temperatures under which this invention is carried out (18 C. to 38 C. or below), and to evaporate readily after application to the puffed borax substrate. Too much volatility will result in excess evaporation before the spray-0n, and insufficient volatility will result in the carrier composition being sticky and nonfree-flowing after the spray-on. Any of the many well known organic liquids, having the above characteristics and being capable of dissolving the water-soluble, waxy solids used in this invention, are suitable for use in the process of this invention.
- Such liquids should have evaporation rates no faster than that of acetone and no slower than that of isopropanol (rates ranging from 110 to 1160). See tables in the Kirk Othmer Encyclopedia of Chemical Technology, volume 12, pages 6667 et seq. (1954), incorporated herein by reference.
- suitable solvents are: lower monohydric alcohols such as methanol, ethanol, propanol and isopropanol, lower ketones such as acetone and methyl ethyl ketone, and low molecular weight esters such as ethyl acetate and isopropyl acetate.
- Organic solvents such as ethyl formate and ethyl ether are too volatile and organic solvents such as cyclohexanone, n-butyl alcohol nbutyl acetate, dimethyl snlfoxide and dimethyl formamide, have boiling points which are too high.
- This invention may be practiced in the following manner.
- the water-soluble waxy material is dissolved in the volatile solvent defined above.
- an amount of fine granular peroxyhydrate salt preferably sodium perborate, which is 0.1 to 1.5 and preferably 0.25 to 1.0 times the weight of the waxy material.
- This slurry is then sprayed through an atomizing nozzle onto a puffed borax substrate of preselected bulk density and particle size distribution the amount of said substrate being from 0.05 to 1.0 and preferably from 0.1 to 0.4 times the combined weight of the water-soluble, waxy solid and peroxyhydrate salt contained in the slurry.
- compositions consisting essentially of about 20% to 88% water-soluble waxy solid, 4.5% to 59% peroxyhydrate salt, and 4.5 to 50% borax.
- the resulting product is a crisp, free-flowing, fast-dissolving granule, comprising a puffed borax substrate with finely divided crystalline peroxyhydrate salt imbedded in an outer coating of water-soluble waxy solid adhering to said substrate.
- EXAMPLE I Seventy-five pounds of the condensation product of one mole of coconut fatty alcohol and moles of ethylene oxide were dissolved in 45 pounds of ethanol. 30 pounds of sodium perborate having a particle size between 0.074 mm. and 0.063 mm. (through No. 200 and on No. 230 Standard U.S. Sieve) was slurried into this solution. This slurry was then sprayed through an atomizing nozzle onto 30 pounds of a puffed borax substrate having a particle size distribution between 1.2 and 0.30 mm, (through 16 mesh and on mesh U.S. Standard Sieve Series), and a bulk density of 0.2 g./ cc. The spray-on was accomplished by spraying the slurry into a falling curtain of puffed borax formed in a rotating baffled drum.
- the resulting product was a crisp, free-flowing, fastdissolving granular carrier comprising approximately coconut alcohol/ethylene oxide condensate, 22.5% perborate and 22.5% puffed borax.
- the carrier had a bulk density of 0.35 g./cc. and a particle size distribution between 1.2 and 0.30 mm., and showed essentially no segregation when mixed with detergent granules of comparable particle size and density.
- EXAMPLE II An oxygen carrier is prepared having the same com position as that in Example I except that the condensation product of one mole tallow fatty alcohol and 30 moles of ethylene oxide is substituted for the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide.
- the process used is identical to that in Example I except that methanol is substituted for ethanol.
- the resulting product is a crisp, free-flowing, fast-dissolving granule showing essentially no segregation when mixed with detergent granules of comparable particle size and density.
- An oxygen carrier of substantially the same characteristics is also obtained when the condensation product of tallow fatty alcohol and 30 moles of ethylene oxide is replaced by the condensation product of nonyl phenol and 15 moles of ethylene oxide, oleyl alcohol condensed with 20 moles of ethylene oxide or tallow fatty acid amide condensed with 15 moles of ethylene oxide.
- a granular oxygen bleach carrier consisting essentially of 4.5% to 59% of a peroxyhydrate salt having a particle size of 0.044 to 0.210 mm. and selected from the group consisting of the peroxyhydrates of the alkali metal borates, carbonates, silicates and phosphates, imbedded in 20% to 88% of a water-soluble, waxy, compound which is solid at temperatures between 18 C. and 38 C.
- composition of claim 1 wherein the peroxyhydrate salt is sodium perborate.
- composition of claim 1 wherein the peroxyhydrate'salt is sodium percarbonate.
- composition of claim 2 wherein the watersoluble waxy solid is selected from the group consisting of solid condensation products of 6-50 moles of ethylene oxide with one mole of any one of the following: (1) fatty alchols of 10-22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 8-12 carbon atoms in the alkyl chain.
- composition of claim 2 wherein the watersoluble, waxy solid is the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide.
- composition of claim 2 wherein the watersoluble, waxy solid is the condensation product of one mole of tallow fatty alcohol and 30 moles of ethylene oxide.
- a process for preparing an oxygen bleach carrier comprising the steps of (a) dissolving a water-soluble, waxy solid, selected from the group consisting of water-soluble compounds which are waxy solids at temperatures between 18" C. and 38 C. and are selected from the group consisting of solid condensation products of 6-50 moles of ethylene oxide with one mole of any one of the following: (1) fatty alcohols of 10-22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 8-12 carbon atoms in the alkyl chain,
- water-soluble, waxy solid is the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide, and the solvent is ethanol.
- waxy solid is the condensation product of one mole of tallow fatty alcohol and 30 moles of ethylene oxide and the solvent is methanol.
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- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A FAST DISSOLVING, NONSEGREGATING OXYGEN CARRIER FOR GRANULAR DETERGENTS IS DISCLOSED, CONSISTING ESSENTIALLY OF 4.5% TO 59% FINELY DIVIDED PEROXYHYDRATE SALT IMBEDDED IN 20% TO 88% OF A WATER-SOLUBLE WAXY SOLID, SAID WAXY SOLID ADHERING TO 4.5% TO 50% OF GRANULAR BORAX SUBSTRATE, SAID SUBSTRATE HAVING A BULK DENSITY OF 0.03 TO 0.56 G/.CC. AND A PARTICLE SIZE BETWEEN 0.074 MM. AND 3.36 MM. A PROCESS FOR PREPARING THE OXYGEN CARRIER IS ALSO DISCLOSED IN WHICH THE WAXY SOLID IS DISSOLVED IN A VOLATILE ORGANIC SOLVENT, THE PEROXYHYDRATE SALT IS SLURRIED INTO THE SOLUTION, AND THE SLURRY IS SPRAYED ONTO A FALLING CURTAIN OF THE GRANULAR BORAX.
Description
3,562,171 OXYGEN CARRKER FOR DETERGENT CGMPUSTTHONS Robert A. Guida, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio N Drawing. Filed Dec. 31, 1968, Ser. No. 789,003 lint. Q1. Clld 7/54 US. Cl. 252-186 Claims ABSTRACT (IF THE DESCLOSURE A fast dissolving, nonsegregating oxygen carrier for granular detergents is disclosed, consisting essentially of 4.5% to 59% finely divided peroxyhydrate salt imbedded in to 88% of a water-soluble waxy solid, said waxy solid adhering to 4.5% to of granular borax substrate, said substrate having a bulk density of 0.03 to 0.56 g./cc. and a particle size between 0.074 mm. and 3.36 mm. A process for preparing the oxygen carrier is also disclosed in which the waxy solid is dissolved in a volatile organic solvent, the peroxyhydrate salt is slurried into the solution, and the slurry is sprayed onto a falling curtain of the granular borax.
This invention relates to a fast-dissolving, non-segregating oxygen bleach carrier designed for mixing with detergent granules, and the process for preparing said oxygen carrier.
Mechanical mixtures of granular detergents, especially spray-dried detergents, and crystalline inorganic peroxyhydrate salts are well known. The peroxyhydrate salt contains hydrogen peroxide bleach within its crystal structure, and therefore serves as a carrier for incorporating active oxygen bleach into detergent compositions. Sodium perborate tetrahydrate is the most common peroxyhydrate salt used in these mixtures These mechanical mixtures, because of differences in density and particle size between the peroxyhydrate salt and the detergent, have the disadvantage of tending to segregate during handling, so that the peroxyhydrate salt is not uniformly distributed throughout the entire composition when it reaches the consumer. If a relatively large particle size of peroxyhydrate salt is used to reduce segregation, difficulty is encountered in dissolving the peroxyhydrate salt when the composition is used by the consumer. If a fine particle size of peroxyhydrate salt is used in order to obtain fast dissolving, unacceptable segregation occurs.
An object of this invention is to formulate a fast-dissolving, oxygen bleach carrier which can be produced at a density and particle size which approximately match that of the detergent granule with which it is to be mixed.
Another object of the invention is to provide an efficient process by which such an oxygen bleach carrier can be made.
The objects of this invention can be accomplished by a process comprising the steps of (1) dissolving a watersoluble, waxy solid in a volatile solvent, (2) adding a finely divided peroxyhydrate salt to the solution to form a slurry and (3) spraying this slurry onto a granular borax substrate of a preselected bulk density and particle size (described hereinafter as puffed borax), said substrate being formed into a falling curtain to receive the spray-on. Upon contact with the puffed borax, the volatile solvent evaporates, leaving behind a crisp, free flowing, fast dissolving granular composition, comprising a puffed borax substrate with finely divided crystalline peroxyhydrate salt imbedded in an outer coating of water-soluble, waxy solid adhering to said substrate.
The puffed borax used in the present invention can 3,562,171 Patented Feb. 9, 1971 be produced by the process disclosed in an article by R. C. Rhees et al., Soap and Chemical Specialties. vol. XLll, January 1966. pages 58-61 and 118-120. This article describes how borax particles which normally have a bulk density of about 1 g./cc., can be made to puff by rapid heating, and thus be greatly reduced in bulk density. By proper selection of operating conditions, the puffed borax can be produced within a wide range of particle size and bulk density, Densities between 0.03 and 0.56 g./cc. have been obtained. To be useful as a substrate for a nonsegregating oxygen carrier intended for mixing with detergent granules, the puffed borax substrate must have a bulk density and particle size such that the resulting carrier has particle characteristics approximating those of the detergent granules with which it is to be mixed. Such detergent granules generally have a particle size within the range of 0.074 mm. to 3.36 mm. (through No. 6 and on No. 200U.S. Standard Sieve Series), and a bulk density of 0.2 to 0.8 g./cc. A nonsegregating oxygen bleach carrier must also have particle size and density which fall within these ranges. The detergent granules with which the oxygen bleach carrier is to be mixed will have a bulk density within the range specified above. However, the detergent will comprise granules which are not uniform in size, but which have a particle size distribution within the range mentioned above. In order to reduce segregation problerns, the bulk density and particle size distribution of the puffed borax substrate should be chosen so that the resulting oxygen bleach carrier will have a bulk density and particle size distribution which match closely those of the detergent granules with which the carirer is mixed. In determining the bulk density of puffed borax to be used as a substrate, due regard must be had to the increase in density which will occur as a result of the addition of organic solid and peroxyhydrate salt to the substrate. Therefore a puffed borax density less than that of the detergent granules will generally be chosen; precisely how much less depends on the amount of peroxyhydrate salt intended to be added to the substrate. For instance, see Example I below. where pufied borax of 0.2 g./cc. bulk density was used to obtain a carrier having a bulk density of 0.35 g./cc. The addition of peroxyhydrate salt to the puffed borax substrate has little effect on the particle size of the substrate, because the peroxyhydrate salt/waxy solid matrix primarily fills the voids in the irregular surface of the puffed borax granules. Therefore, the particle size distribution of the pulled borax chosen for use as a substrate should be approximately the same as that of the detergent granules with which the oxygen bleach carrier is mixed.
In addition to its function as a substrate in the oxygen bleach carrier of the present invention, the borax also serves a useful function as a pH buffer in the detergent composition to which the oxygen bleach carrier is added.
The water-soluble, waxy solid used in the present invention to cause the peroxyhydrate salt to adhere to the puiied borax substrate, can be selected from a wide range of such materials well known in the detergent art. The only requirement is that it be water-soluble and that it be a waxy solid at ambient temperatures (i.e.. at temperatures between 18 C. to 38 C.). Water solubility is necessary to facilitate rapid dissolving 0f the entire carrier composition, and the solid waxy physical state at ambient temperatures is necessary to keep the peroxyhydrate salt in adhesion to the puffed borax substrate, and at the same time keep the oxygen carrier in the form of a dry free flowing granule.
There are many such water-soluble, waxy solids which are suitable for the purpose of this invention, but the more suitable ones are solid condensation products of a low molecular weight alkylene oxide and a hydrophobic moiety. Preferred water-soluble, waxy, solid condensation products are those of 650 moles of ethylene oxide with one mole of any of the following: (1) fatty alcohols of 22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 812 carbon atoms in the alkyl chain. Several specific examples are as follows: lauryl alcohol condensed with 45 moles of ethylene oxide, tallow alcohol condensed with 30 moles of ethylene oxide, oleyl alcohol condensed with 20 moles of ethylene oxide, tallow fatty acid amide condensed with moles of ethylene oxide, and nonyl phenol condensed with 15 moles of ethylene oxide. These materials, in addition to causing the fine particles of peroxyhydrate salt to adhere to the puffed borax substrate, have detergent properties of their own, and therefore contribute to the cleaning performance of the detergent granules to which the oxygen bleach carrier of this invention is added. Also, in causing the peroxyhydrate salt to adhere to the pulfed borax, these waxy materials form a coating around the peroxyhydrate salt thus reducing or preventing undesirable interactions between the peroxyhydrate salt and other ingredients (e.g., enzymes and free water) which may be present in the detergent granule. The above materials have been mentioned only as examples of water-soluble, Waxy solids which are particularly suitable for use in this invention, and there is no intention that the invention be limited to those mentioned. One skilled in the art could readily select many more such water-soluble, waxy solids which would be suitable.
The peroxyhydrate salts used must have a particle size of less than 0.210 mm. (No. 70 U.S. Standard Sieve Series) in order to obtain the fast dissolving carrier of this invention, and greater than 0.044 mm. (No. 325 U.S. Standard Screen) in order to avoid excessive dust problems in handling. Preferably the particle size should be between 0.149 mm. (No. 100 U.S. Standard Sieve Series) and 0.063 mm. (No. 230 U.S. Standard Sieve Series). These salts can be selected from the group consisting of the peroxyhydrates of the alkali metal borates, carbonates, silicates and phosphates, particularly the sodium and potassium salts. These salts are called peroxyhydrates because they contain hydrogen peroxide in their crystalline structure. Well known examples from this group are the sodium perborate and sodium percarbonate commonly used in the detergent industry.
The solvent used in this invention should have a boiling point within the range of about 55 C. to 110 C. so as to be in the liquid state and easily handled at the ambient temperatures under which this invention is carried out (18 C. to 38 C. or below), and to evaporate readily after application to the puffed borax substrate. Too much volatility will result in excess evaporation before the spray-0n, and insufficient volatility will result in the carrier composition being sticky and nonfree-flowing after the spray-on. Any of the many well known organic liquids, having the above characteristics and being capable of dissolving the water-soluble, waxy solids used in this invention, are suitable for use in the process of this invention. Such liquids should have evaporation rates no faster than that of acetone and no slower than that of isopropanol (rates ranging from 110 to 1160). See tables in the Kirk Othmer Encyclopedia of Chemical Technology, volume 12, pages 6667 et seq. (1954), incorporated herein by reference. Specific examples of such suitable solvents are: lower monohydric alcohols such as methanol, ethanol, propanol and isopropanol, lower ketones such as acetone and methyl ethyl ketone, and low molecular weight esters such as ethyl acetate and isopropyl acetate. Organic solvents, such as ethyl formate and ethyl ether are too volatile and organic solvents such as cyclohexanone, n-butyl alcohol nbutyl acetate, dimethyl snlfoxide and dimethyl formamide, have boiling points which are too high.
This invention may be practiced in the following manner. The water-soluble waxy material is dissolved in the volatile solvent defined above. Into this solution is slurried an amount of fine granular peroxyhydrate salt, preferably sodium perborate, which is 0.1 to 1.5 and preferably 0.25 to 1.0 times the weight of the waxy material. This slurry is then sprayed through an atomizing nozzle onto a puffed borax substrate of preselected bulk density and particle size distribution the amount of said substrate being from 0.05 to 1.0 and preferably from 0.1 to 0.4 times the combined weight of the water-soluble, waxy solid and peroxyhydrate salt contained in the slurry. These ranges of ratios result in compositions consisting essentially of about 20% to 88% water-soluble waxy solid, 4.5% to 59% peroxyhydrate salt, and 4.5 to 50% borax. In order to obtain a uniform coating of the slurry on the substrate, it is preferred to form the substrate into a falling curtain, preferably by rotating it in a baffled drum, while the slurry is being sprayed onto it. The resulting product is a crisp, free-flowing, fast-dissolving granule, comprising a puffed borax substrate with finely divided crystalline peroxyhydrate salt imbedded in an outer coating of water-soluble waxy solid adhering to said substrate.
The practice of the invention will be elucidated by the following examples. All parts and percentages herein are by weight unless otherwise specified.
EXAMPLE I Seventy-five pounds of the condensation product of one mole of coconut fatty alcohol and moles of ethylene oxide were dissolved in 45 pounds of ethanol. 30 pounds of sodium perborate having a particle size between 0.074 mm. and 0.063 mm. (through No. 200 and on No. 230 Standard U.S. Sieve) was slurried into this solution. This slurry was then sprayed through an atomizing nozzle onto 30 pounds of a puffed borax substrate having a particle size distribution between 1.2 and 0.30 mm, (through 16 mesh and on mesh U.S. Standard Sieve Series), and a bulk density of 0.2 g./ cc. The spray-on was accomplished by spraying the slurry into a falling curtain of puffed borax formed in a rotating baffled drum.
The resulting product was a crisp, free-flowing, fastdissolving granular carrier comprising approximately coconut alcohol/ethylene oxide condensate, 22.5% perborate and 22.5% puffed borax. The carrier had a bulk density of 0.35 g./cc. and a particle size distribution between 1.2 and 0.30 mm., and showed essentially no segregation when mixed with detergent granules of comparable particle size and density.
If sodium percarbonate is substituted for sodium perborate in the oxygen carrier of this example, with all other conditions remaining the same, a composition with essentially the same characteristics is obtained.
EXAMPLE II An oxygen carrier is prepared having the same com position as that in Example I except that the condensation product of one mole tallow fatty alcohol and 30 moles of ethylene oxide is substituted for the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide. The process used is identical to that in Example I except that methanol is substituted for ethanol. The resulting product is a crisp, free-flowing, fast-dissolving granule showing essentially no segregation when mixed with detergent granules of comparable particle size and density. An oxygen carrier of substantially the same characteristics is also obtained when the condensation product of tallow fatty alcohol and 30 moles of ethylene oxide is replaced by the condensation product of nonyl phenol and 15 moles of ethylene oxide, oleyl alcohol condensed with 20 moles of ethylene oxide or tallow fatty acid amide condensed with 15 moles of ethylene oxide.
What is claimed is:
1. A granular oxygen bleach carrier consisting essentially of 4.5% to 59% of a peroxyhydrate salt having a particle size of 0.044 to 0.210 mm. and selected from the group consisting of the peroxyhydrates of the alkali metal borates, carbonates, silicates and phosphates, imbedded in 20% to 88% of a water-soluble, waxy, compound which is solid at temperatures between 18 C. and 38 C. and are selected from the group consisting of solid condensation products of 6-50 moles of ethylene oxide with one mole of any one of the following: (1) fatty alcohols of -22 carbon atom chain length; ,(2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 8-12 carbon atoms in the alkyl chain, said waxy compound adhering to 4.5% to 50% granular borax having a bulk density between 0.03 and 0.56 g./cc. and a particle size between 0.074 mm. and 3.36 mm.
2. The composition of claim 1 wherein the peroxyhydrate salt is sodium perborate.
3. The composition of claim 1 wherein the peroxyhydrate'salt is sodium percarbonate.-
4. The composition of claim 2 wherein the watersoluble waxy solid is selected from the group consisting of solid condensation products of 6-50 moles of ethylene oxide with one mole of any one of the following: (1) fatty alchols of 10-22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 8-12 carbon atoms in the alkyl chain.
5. The composition of claim 2 wherein the watersoluble, waxy solid is the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide.
6. The composition of claim 2 wherein the watersoluble, waxy solid is the condensation product of one mole of tallow fatty alcohol and 30 moles of ethylene oxide.
7. A process for preparing an oxygen bleach carrier comprising the steps of (a) dissolving a water-soluble, waxy solid, selected from the group consisting of water-soluble compounds which are waxy solids at temperatures between 18" C. and 38 C. and are selected from the group consisting of solid condensation products of 6-50 moles of ethylene oxide with one mole of any one of the following: (1) fatty alcohols of 10-22 carbon atom chain length; (2) fatty acid amides of 10-22 carbon atom chain length and (3) alkyl phenols having 8-12 carbon atoms in the alkyl chain,
6 in a volatile organic solvent having a boiling point between C. and C.,
,(b) slurrying into the solution formed in (a) an amount of peroxyhydrate salt which is 0.1 to 1.5 times the weight of the waxy water-soluble solid in the solution, said peroxyhydrate salt having a particle size between 0.210 mm. and 0.044 mm. and selected from the group consisting of the peroxyhydrates of the alkali metal borates, carbonates, silicates and phosphates, and
(c) spraying the slurry formed in (b) through an atomizing nozzle onto a falling curtain of granular borax having a bulk density between 0.03 g./cc. and 0.56 g./cc. and a particle size between 0.074 mm. and and 3.36 mm., the amount of said borax being from 0.05 to 1 times the combined weight of peroxyhydrate.
salt and waxy water-soluble solid.
8. The process in claim 7 wherein the peroxyhydrate salt is sodium perborate.
9. The process in claim 7 wherein the water-soluble, waxy solid is the condensation product of one mole of coconut fatty alcohol and 45 moles of ethylene oxide, and the solvent is ethanol.
10. The process in claim 7 wherein the water-soluble,
. waxy solid is the condensation product of one mole of tallow fatty alcohol and 30 moles of ethylene oxide and the solvent is methanol.
References Cited UNITED STATES PATENTS 3,018,258 1/1962 Moier et al ll7100 3,154,496 10/1964 Roald 25299 3,255,036 6/1966 Kramer et al. 117100 3,441,507 4/1969 Schiefer et al. 252186 3,449,254 6/1969 Suiter 25299 3,459,665 8/1969 Schiefer et al. 25299 RICHARD D. LOVERING, Primary Examiner I. GLUCK, Assistant Examiner US. Cl. X.R.
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915878A (en) * | 1971-02-09 | 1975-10-28 | Colgate Palmolive Co | Free flowing nonionic surfactants |
US3986987A (en) * | 1974-05-15 | 1976-10-19 | Canada Packers Limited | Light-density, low phosphate, puffed borax-containing detergent compositions |
US4006110A (en) * | 1971-11-30 | 1977-02-01 | Colgate-Palmolive Company | Manufacture of free-flowing particulate heavy duty synthetic detergent composition |
US4289497A (en) * | 1980-09-02 | 1981-09-15 | American Optical Corporation | Gradient photochromic lens and method selectively reducing photochromic activity |
US4547352A (en) * | 1982-03-15 | 1985-10-15 | Capital City Products Company | Reticulated puffed borax having enhanced absorptive capacity |
EP0643130B1 (en) * | 1993-09-13 | 2000-01-19 | The Procter & Gamble Company | Granular detergent compositions comprising nonionic surfactant and process for making such compositions |
US6376453B1 (en) * | 1997-12-10 | 2002-04-23 | Kao Corporation | Detergent particles |
WO2005005588A2 (en) * | 2003-07-15 | 2005-01-20 | A.S.T. Kimya Ve Teknoloji Sanayi Ticaret Limited Sirketi | An anti-foam composition comprising puffed |
-
1968
- 1968-12-31 US US789003A patent/US3562171A/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915878A (en) * | 1971-02-09 | 1975-10-28 | Colgate Palmolive Co | Free flowing nonionic surfactants |
US4006110A (en) * | 1971-11-30 | 1977-02-01 | Colgate-Palmolive Company | Manufacture of free-flowing particulate heavy duty synthetic detergent composition |
US3986987A (en) * | 1974-05-15 | 1976-10-19 | Canada Packers Limited | Light-density, low phosphate, puffed borax-containing detergent compositions |
US4289497A (en) * | 1980-09-02 | 1981-09-15 | American Optical Corporation | Gradient photochromic lens and method selectively reducing photochromic activity |
US4547352A (en) * | 1982-03-15 | 1985-10-15 | Capital City Products Company | Reticulated puffed borax having enhanced absorptive capacity |
EP0643130B1 (en) * | 1993-09-13 | 2000-01-19 | The Procter & Gamble Company | Granular detergent compositions comprising nonionic surfactant and process for making such compositions |
US6376453B1 (en) * | 1997-12-10 | 2002-04-23 | Kao Corporation | Detergent particles |
WO2005005588A2 (en) * | 2003-07-15 | 2005-01-20 | A.S.T. Kimya Ve Teknoloji Sanayi Ticaret Limited Sirketi | An anti-foam composition comprising puffed |
WO2005005588A3 (en) * | 2003-07-15 | 2005-05-06 | T Kimya Ve Teknoloji Sanayi Ti | An anti-foam composition comprising puffed |
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