US3247122A - Detergent tablet and process of preparing same - Google Patents
Detergent tablet and process of preparing same Download PDFInfo
- Publication number
- US3247122A US3247122A US213116A US21311662A US3247122A US 3247122 A US3247122 A US 3247122A US 213116 A US213116 A US 213116A US 21311662 A US21311662 A US 21311662A US 3247122 A US3247122 A US 3247122A
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- US
- United States
- Prior art keywords
- water
- detergent
- soluble
- particles
- tablet
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- 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 claims description 126
- 238000000034 method Methods 0.000 title claims description 23
- 230000008569 process Effects 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 239000002245 particle Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 229920000388 Polyphosphate Polymers 0.000 claims description 14
- 239000001205 polyphosphate Substances 0.000 claims description 14
- 235000011176 polyphosphates Nutrition 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 2
- -1 alkyl phenol Chemical compound 0.000 description 28
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 17
- 239000004484 Briquette Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 230000035939 shock Effects 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 12
- 239000007921 spray Substances 0.000 description 11
- 235000019832 sodium triphosphate Nutrition 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 239000002671 adjuvant Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 206010051602 Laziness Diseases 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- KWVPFECTOKLOBL-KTKRTIGZSA-N 2-[(z)-octadec-9-enoxy]ethanol Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCO KWVPFECTOKLOBL-KTKRTIGZSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 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
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000010338 mechanical breakdown Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- RQFVHGAXCJVPBZ-UHFFFAOYSA-N propylene pentamer Chemical compound CC=C.CC=C.CC=C.CC=C.CC=C RQFVHGAXCJVPBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- DUXXGJTXFHUORE-UHFFFAOYSA-M sodium;4-tridecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 DUXXGJTXFHUORE-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000007916 tablet composition Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000005303 weighing Methods 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
Definitions
- the present invention relates to an improved process for making detergent tablets. More particularly the invented process is of a method of producing such tablets which facilitates their commercial manufacture, even when production must be temporarily interrupted for such causes as mechanical breakdowns, cleaning of equipment and absence of the operator of the processing equipment.
- the invention also includes detergent tablets of a new composition.
- a process for manufacturing a detergent tablet comprises producing a particulate detergent composition comprising about 2 to 20% of a non-cationic synthetic organic detergent, about 25 to 40% of a water soluble polyphosphate, about 20 to 50% of a water soluble metal silicate, about 3.5 to 10% of water soluble sulfate and up to about water, moving and circulating a mass of said particulate detergent, adding 2 to 30% water to the moving and circulating particulate detergent to raise the moisture content thereof to 17 to 30% and lightly compacting the resulting particles to form retaining tablets which are readily disintegrable in wash water, soluble therein and resistant to breakage when subjected to shipping shocks.
- the non-cationic synthetic organic detergent is usually a nonionic detergent, preferably one comprising both hydrophilic and hydrophobic portions in the molecule of which at least the hydrophilic portion includes a plurality of lower joined alkylene oxide groups.
- a preferred detergent of this type is an alkyl phenol having a poly lower alkoxy alkanol joined to the phenolic oxygen.
- Nonyl phenoxy polyoxyethylene ethanol, comprising about 9 to 10 ethoxy groups, has been found to be an excellent nonionic detergent of the present invention.
- the alkyl group may be of 6 to 14 carbon atoms and the alkoxy chain may be of 4 to 12 alkoxy units, each unit comprising from 2 to 4 carbon atoms.
- nonionic detergents including the block copolymers of ethylene oxide and 'propylene Patented Apr. 19, 1966 oxide (Pluronics), reaction products of higher fatty alcohols and lower alkylene oxide (Emulphogene), polyoxyethylated higher fatty acids (Emulphor), polyethoxy and poly lower alkoxy esters and ethers of poly alcohols, especially of sorbitol and mannitol (Span, Tween) may be used with the alkyl phenoxy polyoxyalkylene alkanol and in replacement thereof, where desired.
- nonionics including the block copolymers of ethylene oxide and 'propylene Patented Apr. 19, 1966 oxide (Pluronics), reaction products of higher fatty alcohols and lower alkylene oxide (Emulphogene), polyoxyethylated higher fatty acids (Emulphor), polyethoxy and poly lower alkoxy esters and ethers of poly alcohols, especially of sorbitol and mannitol (Span
- the proportion should be within the range of 2 to 20%, preferably 5 to 15 or 6 to 14% of the detergent briquette. All percentages of constituents in this specification and in the appended claims are on a tablet weight basis.
- nonionic detergent In addition to the nonionic detergent one may have present in the detergent tablet, as replacement of some of the nonionic detergent, an anionic detergent, usually added primarily to produce additional foam, when desired and to contribute its cleaning power to the composition. In some cases it may be found desirable to replace nonionic detergent with a suitable anionic material.
- a preferred anionic detergent is sodium alkyl benzene sulfonate, especially sodium tridecyl benzene sulfonate. This material is a mixture of detergents produced by alkylating benzene with a blend of propylene tetramer and pentamer.
- the alkyl groups are highly branched but other alkyls of relatively straight chain configuration are also useful in these compounds, providing that they are of 12 to 18 carbon atoms.
- the anionic detergents are generally employed as their water soluble sodium salts but other Water soluble metallic salts, such as the alkali metal salts, e.g., potassium salts, may be used too, usually in partial replacement of some of the sodium salt.
- alkyl aryl sulfonates other anionic organic detergents of the sulfated or sulfonated type are useful.
- sodium lauryl sulfate sodium coconut oil fatty acids monoglyceride sulfate and sodium salts of a higher fatty acid amide of N-methyl taurine. It will be seen that these compounds contain a fatty alkyl or acyl group of 10 to 18 carbon atoms, as the lipophilic portion of the molecule and are utilized as their water soluble salts, preferably alkali metal salts.
- the proportion of anionic detergent which may be used to make a detergent tablet is complementary to that of the nonionic detergent. In other words, the sum of both types of detergent material present should not be in excess of about 20% and not less than about 2% of the detergent briquette.
- the water soluble metal silicate is a constituent of the present briquette which has the unusual effect of aiding the production of a briquette which-is form-retaining and resistant to breakage, although pressed at a low pressure,
- silicates allow making of tablets of low bulk density and do not require coating of the tablets.
- those which are alkali metal salts, especially sodium silicates, and which are of a ratio of metal oxide to silica, by weight, of about 0.3 to 0.6 are most often used.
- a highly preferred silicate is sodium metasilicate having a Na O:SiO ratio of 1:235.
- other silicates of the general type described may also be included in the present briquettes, either together with or in replacement of this particular silicate, to obtain similar effects.
- the water soluble polyphosphate is a metal salt, usually an alkali metal salt and preferably the sodium salt of a polyphosphoric acid.
- the most preferable are pentasodium tripolyphosphate and tetrasodium pyrophosphate.
- Other polyphosphates of satisfactory builder action which also enable one to produce improved briquettes, according to the present invention, may be employed in mixture with the described sodium polyphosphates or in replacement thereof. Either the sodium or potassium salts of these materials are used, depending upon the particular properties of the final product desired.
- the water soluble sulfate is the material which, when presentin the detergent particles to be moistened, together with the other detergents and builders mentioned, has the unexpectedly beneficial effect of improving processing properties markedly.
- the sulfate is usually an inorganic compound, generally a metal salt. Most preferred of these is sodium sulfate but other alkali metal sulfates, e.g., potassium sulfate, may be employed providing that they have the same general effect with the composition to which they are added. In addition to the four constituents described, water must be present in the final tablets. Also, adjuvants which are useful to give the detergent briquette special desirable properties may be ineluded. Among such substances are additional builders, foam enhancers or suppressors, coloring agents, per fumes, bleaches, solvents, fluorescent dyes, anti-redeposition agents and so forth. The total proportion of adjuvants employed should be a minor one, to avoid any interference with the desirable physical properties of the detergent briquette.
- the proportions of non-cationic detergent, silicate, polyphosphate, sulfate and water should be regulated in accordance with the following teachings so as to obtain a product which can be economically and efficiently manufactured by the method herein described and which will still be of satisfactory strength and solubility properties.
- the proportion of the synthetic organic detergent should be held within the range of 2 to 20% and is preferably 6 to 14%, most preferably about It has been found that, in conjunction with the silicate and phosphate, such a percentage of organic detergent will give excellent cleaning results and will not interfere with the production of a strong, yet quickly dissolving tablet. Lesser proportions than the minimum of this detergent will not have a satisfactory cleaning effect and higher proportions will often interfere with the desired tablet properties.
- the water soluble phosphate present should be 25 to 40% of the briquette, preferably about 30%.
- Such percen tages of these materials contribute excellent building and detergent properties to the product and complement the silicate to allow the production of a quick dissolving tablet of adequate strength and abrasion resistance.
- such proportions of the polyphosphate may be completely hydrated by some of the water present, leaving additional moisture to aid in making the silicate more readily soluble in the wash water.
- the water oluble silicate comprises to 50% of the briquette andit has been found that such a proportion of silicate is desired to obtain a product which will dissolve rapidly and yet which will be of excellent resistance to breakage during normal shipping.
- a preferred proportion of silicate is 20 to 40% and about 30% is considered best.
- the silicate constituent of these products when employed in these proportions, exhibits a dramatic effect in modifying the tablet properties, making the tablet lighter, yet stronger, helping the particles to be joined together more tightly, so as to diminish a tendency to break under rough handling, yet promoting very rapid solubility. These beneficial results may be obtained without surface coating the detergent briquettes, which is unexpected.
- the proportion of Water present in these briquettes is important to obtain a satisfactory product having the properties discussed previously.
- the water substantially or completely hydrates the polyphosphate and also greatly improves the solubility of the silicate, so that virtually no insoluble grains are found in wash water into which briquettes have been placed. Seventeen to 30% of water in the invented briquettes will accomplish these results and it is preferred to employ 19 to of water in most of the invented compositions, most preferably 21 to 23% whereby substantial hydration, e.g., 75% hydration or more, of the polyphosphate takes place.
- Moisture added to the particulate 4 detergent is 2 to 30%, preferably 7 to 17%. It has been found that within the ranges mentioned more water can be included in the briquettes when silicates of lower ratios of Na O:SiO within the 0.3 to 0.6 range, are used.
- the proportion of sodium sulfate in the detergent tablets to obtain improved processing properties is from 3.5 to 10%. This may be obtained by producing a particulate detergent having about 4 to 12% sodium sulfate therein, allowance being made for the decrease in the proportion of the sodium sulfate caused by addition of moisture.
- the same percentage ranges were given for both the final tablet and the particulate detergent composition from which it is made, to avoid unnecessary inclusion of additional ranges of constituents in the particulate detergent. It is understood that the ranges given primarily describe the final product and the crutcher mix composition and particulate detergent composition will usually be chosen accordingly.
- a particulate detergent is produced in which the organic detergent, sulfate, silicate and. polyphosphate are present. It is highly preferred that such detergent composition constituents be homogeneously distributed throughout the articles and spray dried detergent beads have been found to be an excellent starting material for making these briquettes.
- spray drying operation one makes a solution or slurry of the detergent materials in an aqueous medium, usually adding to this crutcher mlx useful adjuvant substances which are not adversely affected by spray drying. Normally, the crutcher mix will be of a solids content within the range of about 40 to 60%.
- This aqueous dispersion or solution is then pumped through spray nozzles and is dried in a path of heated drying gas, through which it usually falls to a collector.
- the particles produced may be cooled, screened and classified to remove objectionably large or small material.
- the product resulting may be somewhat irregular in shape but is usually considered to be composed of bodies which are hollow and of approximately spherical shape. Those of particle size such that over pass through an 8 mesh sieve and do not pass a mesh sieve, a US. Standard Sieve Series, are excellent beads to be converted into briquettes or tablets.
- Most of the Water present in the crutcher mix is removed but there may be left in the particles up to about 15% of moisture, and usually at least 1% is present.
- the homogeneous detergent composition particles may be produced by other methods than spray drying. For example, spray cooling, agglomeration, even crushing, followed by screening and classification, may be employed to produce the desired particles. Also, a portion of the product may be spray dried and to this may be separately added organic detergent, silicate and phosphate. However, it is considered important to have a substantial proportion of the silicate present, at least about 75% thereof, present with the phosphate and organic detergent and distributed throughout each of the particles, as in a spray dried composition.
- the particles of detergent composition, high in silicate content, as described above, are placed in continuous motion as in la tumbling drum, and while moving, moisture is sprayed onto the particle surfaces in fine droplet form and in amount to produce a final product having a moisture content of 17 to 30%, preferably 19 to
- the continuously moving and circulating particles may adhere lightly to a number of other particles, in the course of spraying and circulating them.
- the detergent beads are of an apparent density of about 0.2 to 0.6 gram per cubic centimeter. After moistening, this density may be altered somewhat, usually being decreased, e.g., by as much as This result is attributable to the moistening of the relatively large proportions of silicate together with polyphosphate and the resulting swelling of materials and increase in average particle size.
- Adequate and uniform moistening of the detergent beads or granules high in silicate content maintain the silicate in a readily soluble condition so that no undissolved silicate deposits on clothing being Washed. This is of importance to the detergent chemist because silicates tend to become more insoluble when heated to drive off the moisture accompanying them, as is done in spray drying. Also, the polyphosp'hates preferentially attract moisture, thereby often tending to reduce the silicate to a less soluble state. Even when placed in an excess of water, as in the washing machine, such silicates may not dissolve completely during the wash cycle, leading to objectionable particles left on the articles being laundered.
- any silicate of lower solubility is soon made more soluble.
- This more soluble form or condition persists for long periods of time after moistening, and the briquette produced therefrom is still completely soluble, months after it is made.
- a most even distribution of moisture in the detergent and an absence of excessive agglomeration are noted when the material beingmoistened is kept in continuous motion and the moisture is applied in fine droplet form.
- Mixing, moistening, and agglomeration to a desired extent may be followed by screening the pressed detergent to desired particle size range. It has been found preferable to have the particles between 4 and 40 mesh, US.
- Standard Sieve Series Standard Sieve Series, but other size ranges may be utilized.
- moisture When moisture is added to particles initially of very low moisture content, it has been usually found more difiicult to add large proportions of moisture, within the ranges mentioned, than to add lesser amounts thereof. Also, it is usually desirable to add more than the minimal proportion of moisture when the particles are initially comparatively dry.
- the operator of the mixing equipment will normally adjust his mixing techniques, speeds, and times to produce the most desirable moistening of the detergent particles.
- two-step addition of moisture may be found desirable, wherein an initial amount of moisture is added, mixed for a sufficient length of time, perhaps 5 minutes to as long as one-half hour, and then a second addition of moisture is made.
- mixing speeds may be adjusted, as may mixing times. However, mixing speeds of 100 to 250 lineal feet per minute, at the exterior of a rotating drum, equipped with internal bafiies have been found useful. Mixing times of as little as one minute can give acceptably moistened detergent particles.
- the moistened product Due to the presence of the sulfate in this composition, the moistened product is not sensitive to undesired aggregation into lumps or concrete masses. Thus, the moistened detergent may be held as long as an hour or more in some instances and will still be free flowing, suitable for transport to the press.
- the reason for the unexpected effect of the rather specific proportions of sulfate is not known, although it is theorized that the sulfate enters into and regulates the speed of hydration of the other salts present, thereby changing the type of aggregate produced.
- the pressure employed may be any suitable low pressure, it having been found that pressures from 3 to 25 pounds per square inch may be used advantageously in pressing a table, which is most often from about A to 1 inch thick. Pressures over pounds per square inch should be avoided. Pressing is preferably effected between opposed dies having Teflon or chrome plated surfaces and cavities. After pressing, it is unnecessary to submit the product made to any special treatment or aging period before it may be shipped although as ignificant increase in strength is observed within about an hour after pressing.
- the detergent briquettes prepared are of suflicient strength to withstand shipping without breaking or being severely abraded and they may be packed in any usual way. It has been noted that the briquettes made often have highly desirable low densities, making a tablet whose larger volume is easier for the user to employ and which facilitates subdivision into small units, where accurate control of the detergent concentration employed is considered important. It is considered unpredictable that the detergent powder and tablet bulk densities should be of such desired low densities in the claimed formulas, from 0.2 to 0.6 gram per cubic centimeter, since previous observation indicated that sulfates tended to increase such densities. Surprisingly, too, the lighter briquettes are even stronger than comparable heavier materials made with less silicate.
- the moistening solution may include adjuvant materials not stable to heat, e.g., emulsified perfumes.
- Products produced may subsequently be perfumed, colored, wrapped and packed for shipment. It is preferred to pack them in moisture tight wrappers, e.g., sleeves of polyethylene film, but they are still resistant to breakage and are usefully soluble, even when stored for months at atmospheric conditions.
- a briquette can stand at least five shocks equivalent to a free fall of four feet onto a hard surface before it starts to break apart. Also, when packed in polyethylene sleeves, the briquettes do not become abraded objectionably, despite repeated shaking in a package, which simulates a type of rough handling to which they may be subjected in shipping. Still, despite their great strength,
- the tablets dissolve quickly and completely, usually disintegrating completely within 45 seconds and most often in 10 to 30 seconds.
- the following examples are included to illustrate embodiments of the invented process and products. They are not to be considered as limiting the invention. All proportions are by weight, unless otherwise indicated.
- An equeous crutcher mix was made of all the above materials except the pigment and the approximately 55% solids mix was sprayed at a pressure of about 300 pounds per square inch and at a temperature of 135 F. into heated drying gas at an initial temperature of about 600 F.
- the particles obtained, of about 8 to 100 mesh, were of a moisture content of about 10%. They were sprayed with a fine spray of water while being tumbled for to minutes in a slightly tilted drum rotating at a peripheral linear speed of about 100 to 250 feet per minute.
- Sprayed product was continuously removed at a moisture content of 21% and was screened to 4 to 40 mesh (through 4, on 40 mesh), after which it was held for periods up to an hour and pressed. This product may also be held several hours and is still pressable. It does not lump objectionably on storage.
- the powder before pressing is of a bulk density of about 0.25 gram per cubic centimeter, the spray dried powder being approximately 0.3 gram per cubic centimeter. It is pressed to a chamfered flat cylinderical tablet of 2% inches diameter by 0.815 inch thickness, weighing 1.3 ounce, being of a bulk density of about 0.5 gram per cubic centimeter. Pressing was at a pressure of about 5 to 25 pounds per square inch.
- the tablet made was an excellent laundry detergent. It was quickly disintegrable in wash water in a typical washing machine. When tested by dropping 2 feet onto an end, immediately after manufacture it did not break up. After aging several hours or overnight the tablet strength even increases, as it does when 2 to.5% moisture is sprayed onto the tablet surface followed by drying off of such added moisture.
- the above formula is for a detergent briquette processable by the method of Example II.
- the product obtained is acceptable as a laundry detergent tablet, although the detergent particles produced are of higher bulk density than those made with more silicate. In part, this effect may be attributable to the spray properties of the crutcher mix and subsequent differences in moistening effects.
- the detergent particles processed well and did not lump objectionably or exhibit a laziness after standing.
- Example IV A tablet of formula like that of Example II was made, except for replacement of the 3.5 parts sodium sulfate with 10.0 parts and the changing of the moisture content to 23%. The product produced was comparable to that of Example II and processed readily, exhibiting no laziness.
- a process for manufacturing a detergent tablet which comprises producing a particulate detergent composition comprising 2 to 20% of a water-soluble synphilic and hydrophobic portions in the molecule in which at least the hydrophilic portion includes a plurality of lower joined alkylene oxide groups or mixtures thereof, 25 to 40% of a water-soluble alkali metal polyphosphate, 20 to 50% of a water-soluble alkali metal silicate, 4 to 12% of a water-soluble alkali metal sulfate and up to about 15% water, moving and circulating a mass of said particulate detergent, adding 2 to 30% water to the moving and circulating particulate detergent to raise the moisture content thereof to 17 to 30% whereby the moisture is substantially uniformly distributed throughout the mass of said particles. and lightly compacting the resulting particles at a pressure of 3-100 p.s.i. into form retaining tablets which are readily disintegrable in wash water, soluble therein and resistant to breakage when subjected to shipping shocks.
- a process for manufacturing a detergent tablet which comprises spray drying a particulate detergent composition comprising 2 to 20% of a water-soluble nonionic detergent containing both hydrophilic and hydrophobic portions in the molecule in which at least the hydrophilic portion include-s a plurality of lower joined alkylene oxide groups or mixtures thereof, 25 to 40% of a water-soluble alkali metal polyphosphate selected from the group consisting of pyroph'osphates and tripolyphosphates, 20 to 50% of a water-soluble alkali metal silicate having a metal oxide to silica ratio between 0.3 and 0.6, 4 to 12% of water-soluble alkali metal sulfate and up to water, moving and circulating a mass of said particulate detergent, adding 2' to 30% water to the moving and circulating particulate detergent to raise the moisture content thereof to 17 to 30% whereby the moisture is substantially uniformly distributed throughout the mass of said particles and lightly compacting the resulting particles at a pressure of 3-100 p.s.i. into form retaining tablets
- a process for manufacturing a detergent tablet which comprises spray drying a particulate detergent composition comprising 6 to 14% of a nonionic synthetic organic detergent which is a higher alkyl phenol poly lower alkoxy alkanol, 25 to 40% of a water-soluble alkali metal tripolyphosphate, to 40% of a watersoluble alkali metal silicate of metal oxide to silica ratio between about 0.3 and 0.6, 4 to 12% of water-soluble alkali metal sulfate and up to 15 water, moving and circulating a mass of said particulate detergent, adding 2 to 30% water to the moving and circulating particulate detergent to raise the moisture content thereof to 17 to 30% whereby the moisture is substantially uniformly distributed throughout the mass of said particles and lightly compacting the resulting particles at a pressure of 3-100 p.s.i. into form retaining tablets which are readily disintegrable in water, soluble therein and resistant to breakage when subjected to shipping shocks.
- a particulate detergent composition comprising 6 to 14% of a nonionic
- a process for manufacturing a detergent tablet which comprises making an aqueous mixture of a detergent composition comprising 6 to 14% of a nonyl phenol polyoxyethylene ethanol in which the polyoxyethylene ethanol is of 9 to 10 oxyethylene units, to 40% sodium tripolyphosphate, 20 to 40% sodium silicate of Na O:SiO ratio of about 0.4, 4 to 12% of sodium sulfate and 8 to 12% water, spray drying the aqueous mixture in a heated drying gas to a particulate detergent of such composition, moving and circulating a mass of said particulate detergent, adding 7 to 17% water to the moving and circulating particulate detergent to raise the moisture content thereof to 19 to 25% whereby the moisture is substantially uniformly distributed throughout the mass of said particles and lightly compacting the resulting particles at a pressure of 3 to 25 p.s.i. into form retaining tablets of a bulk density between about 0.3 and 0.5 grams per cubic centimeter, said tablets being readily disintegrable in water, soluble therein and resistant to breakage when subjecte
- a process for manufacturing a detergent tablet which comprises making an aqueous mixture of a detergent composition comprising about 10% of nonyl phenol polyoxyethylene ethanol in which the polyoxyethylene ethanol averages about 9.5 oxyethylene units per molecule, about sodium tripolyphosphate, about 30% of sodium silicate of Na O:SiO ratio of about 1:2.35, about 7% of sodium sulfate and about 10% water, all percentages being on a final product basis except that for water, mixing the aqueous composition to distribute the various constituents thereof evenly, spraying the homogeneous mixture under pressure in fine droplet form into a drying gas and drying said droplets to particles substantially between 8 and 100 mesh and of bulk density of about 0.2 to 0.6 gram per cubic centimeter, moving and circulating a mass of said particulate detergent, adding about 12% water to the moving and circulating particulate detergent to raise the moisture content thereof to about 22% whereby the moisture is substantially uniformly distributed throughout the mass of said particles and lightly compacting the resulting particles at a pressure of 3-25
- a detergent tablet which comprises 2 to 20% of a water-soluble synthetic organic detergent selected from the group consisting of sulfated and sulfonated anionic detergents and nonionic detergents containing hydrophilic and hydrophobic portions in the molecule of which at least the hydrophilic portion includes a plurality of lower joined alkylene oxide groups or mixtures thereof, 25 to 40% of a water soluble alkali metal polyphosphate, 20 to 50% of a water soluble alkali metal silicate, 3.5 to 10% of water soluble alkali metal sulfate and 17 to 30% water, the tablet being in the form of particles compacted at a pressure of 3-100 p.s.i., which tablet is disintegrable in wash water, soluble therein, form retaining and resistant to breakage when subjected to shipping shocks.
- a water-soluble synthetic organic detergent selected from the group consisting of sulfated and sulfonated anionic detergents and nonionic detergents containing hydrophilic and hydrophobic portions in the molecule
- a detergent tablet which comprises 6 to 14% of a nonionic synthetic organic detergent which is a higher alkyl phenol poly lower alkoxy alkanol, 25 to 40% of a water soluble alkali metal tripolyphosphate, 20 to 40% of a water soluble alkali metal silicate of metal oxide to silica ratio between about 0.3 and 0.6, 3.5 to 10% of water soluble alkali metal sulfate and 17 to 30% water, the tablet being in the form of particles compacted at a pressure of 3-100 p.s.i., which tablet is of a bulk density between about 0.3 to 0.5 gram per cubic centimeter, form retaining and resistant to breakage when subjected to shipping shocks and also floats in wash water, disintegrates rapidly therein and is substantially completely soluble therein.
- a nonionic synthetic organic detergent which is a higher alkyl phenol poly lower alkoxy alkanol
- a water soluble alkali metal tripolyphosphate 20 to 40% of a water soluble al
- a detergent tablet which comprises 6 to 14% of a nonyl phenol polyoxyethylene ethanol in which the polyoxyethylene ethanol is of 9 to 10 oxyethylene units, 25 to 40% sodium tripolyphosphate, 20 to 40% sodium silicate of Na O:SiO ratio of about 0.4, 3.5 to 10% of sodium sulfate and 10 to 25% water, the tablet being in the form of spray dried particles compacted at a pressure of 3-100 p.s.i., which tablet is of a bulk density between about 0.3 and 0.5 gram per cubic centimeter, form retaining and resistant to breakage when subjected to shipping shocks and also floats in wash water, disintegrates rapidly therein and is substantially completely soluble therein.
- a detergent tablet which comprises about 10% of nonyl phenol polyoxyethylene ethanol in which the polyoxyethylene ethanol averages about 9.5 oxyethylene units per molecule, about 30% of sodium tripolyphosphate, about 30% of sodium silicate of Na O:Si0 ratio of about 1:2.35, about 7% of sodium sulfate and about 22% Water, the tablet being in the form of spray dried particles compacted at a pressure of 3-100 p.s.i., which tablet is of a bulk density between about 0.3 and 0.5 gram per cubic centimeter, form retaining and resistant to breakage when subjected to shipping shocks and also floats in wash water, disintegrates rapidly therein and is substantially completely soluble therein.
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- 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)
Priority Applications (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA718384A CA718384A (en) | 1962-07-30 | Manufacture of detergent tablets | |
CA718383A CA718383A (en) | 1962-07-30 | Manufacture of detergent tablets | |
NL295937D NL295937A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1962-07-30 | ||
BE635589D BE635589A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | 1962-07-30 | ||
US213116A US3247122A (en) | 1962-07-30 | 1962-07-30 | Detergent tablet and process of preparing same |
US213117A US3247123A (en) | 1962-07-30 | 1962-07-30 | Manufacture of detergent tablets |
AU32790/63A AU3279063A (en) | 1962-07-30 | 1963-07-09 | Manufacture of detergent tablets |
ES290152A ES290152A1 (es) | 1962-07-30 | 1963-07-20 | Procedimiento para la fabricación de tabletas detergentes |
DE19631467564 DE1467564A1 (de) | 1962-07-30 | 1963-07-22 | Verfahren zur Herstellung von Waschmitteltabletten |
DK348663AA DK117972B (da) | 1962-07-30 | 1963-07-22 | Fremgangsmåde til fremstilling af brudsikre vaskemiddeltabletter. |
GB29355/63A GB995940A (en) | 1962-07-30 | 1963-07-24 | Manufacture of detergent tablets |
FR942621A FR1387029A (fr) | 1962-07-30 | 1963-07-25 | Procédé de préparation de pains de détergent |
CH928563A CH439554A (de) | 1962-07-30 | 1963-07-25 | Verfahren zur Herstellung von Waschmitteltabletten |
BR151230/63A BR6351230D0 (pt) | 1962-07-30 | 1963-07-29 | Processo para fabricar um tablete de detergente e respectivo tablete de detergente |
MY196698A MY6600098A (en) | 1962-07-30 | 1966-12-31 | Manufacture of detergent tablets |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US213117A US3247123A (en) | 1962-07-30 | 1962-07-30 | Manufacture of detergent tablets |
US213116A US3247122A (en) | 1962-07-30 | 1962-07-30 | Detergent tablet and process of preparing same |
Publications (1)
Publication Number | Publication Date |
---|---|
US3247122A true US3247122A (en) | 1966-04-19 |
Family
ID=26907784
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US213116A Expired - Lifetime US3247122A (en) | 1962-07-30 | 1962-07-30 | Detergent tablet and process of preparing same |
US213117A Expired - Lifetime US3247123A (en) | 1962-07-30 | 1962-07-30 | Manufacture of detergent tablets |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US213117A Expired - Lifetime US3247123A (en) | 1962-07-30 | 1962-07-30 | Manufacture of detergent tablets |
Country Status (13)
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3370015A (en) * | 1964-01-30 | 1968-02-20 | Lever Brothers Ltd | Process for preparing detergent compositions |
US3383321A (en) * | 1965-03-09 | 1968-05-14 | Procter & Gamble | Detergent tablets |
US3709837A (en) * | 1970-12-30 | 1973-01-09 | Philadelphia Quartz Co | Spray dried detergents containing sodium-potassium double silicate |
US4022704A (en) * | 1971-06-21 | 1977-05-10 | Stauffer Chemical Company | Production of spray dried, high bulk density hydrous sodium silicate mixtures |
US4219435A (en) * | 1977-11-27 | 1980-08-26 | The Procter & Gamble Company | Detergent tablet coating |
US5078301A (en) * | 1987-10-02 | 1992-01-07 | Ecolab Inc. | Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use |
US5234615A (en) * | 1987-10-02 | 1993-08-10 | Ecolab Inc. | Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use |
US5552079A (en) * | 1993-09-13 | 1996-09-03 | Diversey Corporation | Tableted detergent, method of manufacture and use |
US5952279A (en) * | 1994-09-09 | 1999-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Mild detergent mixtures |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3455834A (en) * | 1964-01-22 | 1969-07-15 | Colgate Palmolive Co | Process for production of detergent tablets |
US3392120A (en) * | 1964-03-19 | 1968-07-09 | Fmc Corp | Dry detergent mixtures |
US3360469A (en) * | 1965-06-07 | 1967-12-26 | Fmc Corp | Dry-mixed detergent compositions |
US3361675A (en) * | 1965-08-23 | 1968-01-02 | Fmc Corp | Dry-mixed detergent compositions |
US3408300A (en) * | 1965-12-13 | 1968-10-29 | Henkel & Cie Gmbh | Stable,alkaline,non-forming cleansing agents |
US4370250A (en) * | 1976-12-06 | 1983-01-25 | Colgate-Palmolive Company | Detergent tablet |
US4451386A (en) * | 1976-12-06 | 1984-05-29 | Colgate-Palmolive Company | Detergent tablet |
DE3541145A1 (de) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | Einheitlich zusammengesetzte reinigungsmitteltabletten fuer das maschinelle geschirrspuelen |
DE4010533A1 (de) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung |
DE19709411A1 (de) * | 1997-03-07 | 1998-09-10 | Henkel Kgaa | Waschmittelformkörper |
US20160221884A1 (en) * | 2013-09-18 | 2016-08-04 | Technion Research & Development Foundation Ltd. | Concrete formulations and admixtures therefor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA510555A (en) * | 1955-03-01 | C. Miller Robert | Detergent compositions | |
US2875155A (en) * | 1954-12-09 | 1959-02-24 | Colgate Palmolive Co | Detergent briquette and process for the production thereof |
US3081267A (en) * | 1959-12-31 | 1963-03-12 | Procter & Gamble | Detergent tablet and process for making same |
-
0
- BE BE635589D patent/BE635589A/xx unknown
- NL NL295937D patent/NL295937A/xx unknown
- CA CA718383A patent/CA718383A/en not_active Expired
- CA CA718384A patent/CA718384A/en not_active Expired
-
1962
- 1962-07-30 US US213116A patent/US3247122A/en not_active Expired - Lifetime
- 1962-07-30 US US213117A patent/US3247123A/en not_active Expired - Lifetime
-
1963
- 1963-07-09 AU AU32790/63A patent/AU3279063A/en not_active Expired
- 1963-07-20 ES ES290152A patent/ES290152A1/es not_active Expired
- 1963-07-22 DE DE19631467564 patent/DE1467564A1/de active Pending
- 1963-07-22 DK DK348663AA patent/DK117972B/da unknown
- 1963-07-24 GB GB29355/63A patent/GB995940A/en not_active Expired
- 1963-07-25 FR FR942621A patent/FR1387029A/fr not_active Expired
- 1963-07-25 CH CH928563A patent/CH439554A/de unknown
- 1963-07-29 BR BR151230/63A patent/BR6351230D0/pt unknown
-
1966
- 1966-12-31 MY MY196698A patent/MY6600098A/xx unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA510555A (en) * | 1955-03-01 | C. Miller Robert | Detergent compositions | |
US2875155A (en) * | 1954-12-09 | 1959-02-24 | Colgate Palmolive Co | Detergent briquette and process for the production thereof |
US3081267A (en) * | 1959-12-31 | 1963-03-12 | Procter & Gamble | Detergent tablet and process for making same |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3370015A (en) * | 1964-01-30 | 1968-02-20 | Lever Brothers Ltd | Process for preparing detergent compositions |
US3383321A (en) * | 1965-03-09 | 1968-05-14 | Procter & Gamble | Detergent tablets |
US3709837A (en) * | 1970-12-30 | 1973-01-09 | Philadelphia Quartz Co | Spray dried detergents containing sodium-potassium double silicate |
US4022704A (en) * | 1971-06-21 | 1977-05-10 | Stauffer Chemical Company | Production of spray dried, high bulk density hydrous sodium silicate mixtures |
US4219435A (en) * | 1977-11-27 | 1980-08-26 | The Procter & Gamble Company | Detergent tablet coating |
US5078301A (en) * | 1987-10-02 | 1992-01-07 | Ecolab Inc. | Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use |
US5234615A (en) * | 1987-10-02 | 1993-08-10 | Ecolab Inc. | Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use |
US5552079A (en) * | 1993-09-13 | 1996-09-03 | Diversey Corporation | Tableted detergent, method of manufacture and use |
US5952279A (en) * | 1994-09-09 | 1999-09-14 | Henkel Kommanditgesellschaft Auf Aktien | Mild detergent mixtures |
Also Published As
Publication number | Publication date |
---|---|
DK117972B (da) | 1970-06-22 |
ES290152A1 (es) | 1963-10-16 |
US3247123A (en) | 1966-04-19 |
BE635589A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | |
CA718384A (en) | 1965-09-21 |
DE1467564A1 (de) | 1969-10-09 |
FR1387029A (fr) | 1965-01-29 |
CA718383A (en) | 1965-09-21 |
AU3279063A (en) | 1965-01-14 |
NL295937A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) | |
BR6351230D0 (pt) | 1973-08-28 |
GB995940A (en) | 1965-06-23 |
MY6600098A (en) | 1966-12-31 |
CH439554A (de) | 1967-07-15 |
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