US3247123A - Manufacture of detergent tablets - Google Patents
Manufacture of detergent tablets Download PDFInfo
- Publication number
- US3247123A US3247123A US213117A US21311762A US3247123A US 3247123 A US3247123 A US 3247123A US 213117 A US213117 A US 213117A US 21311762 A US21311762 A US 21311762A US 3247123 A US3247123 A US 3247123A
- Authority
- US
- United States
- Prior art keywords
- water
- detergent
- soluble
- tablet
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims description 123
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000002245 particle Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 36
- 229920000388 Polyphosphate Polymers 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000001205 polyphosphate Substances 0.000 claims description 22
- 235000011176 polyphosphates Nutrition 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-PWCQTSIFSA-N Tritiated water Chemical compound [3H]O[3H] XLYOFNOQVPJJNP-PWCQTSIFSA-N 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 239000004484 Briquette Substances 0.000 description 21
- -1 alkyl phenol Chemical compound 0.000 description 18
- 239000000463 material Substances 0.000 description 15
- 238000003825 pressing Methods 0.000 description 10
- 235000019832 sodium triphosphate Nutrition 0.000 description 10
- 239000007921 spray Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 150000004760 silicates Chemical class 0.000 description 8
- 239000002671 adjuvant Substances 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- 239000011324 bead Substances 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 229910052911 sodium silicate Inorganic materials 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052914 metal silicate Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- SUZRRICLUFMAQD-UHFFFAOYSA-N N-Methyltaurine Chemical compound CNCCS(O)(=O)=O SUZRRICLUFMAQD-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
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 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
- 239000012467 final product Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000271 synthetic detergent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- 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
- 229920005682 EO-PO block copolymer Polymers 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 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
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 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
- 238000011160 research Methods 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 238000012216 screening Methods 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
- OFGIQHQRUSYPOU-UHFFFAOYSA-N sodium;tridecylbenzene Chemical compound [Na].CCCCCCCCCCCCCC1=CC=CC=C1 OFGIQHQRUSYPOU-UHFFFAOYSA-N 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
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000007916 tablet composition Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000002087 whitening effect Effects 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 a detergent tablet which is readily disintegrable in water and dissolves completely therein, while being of sufiicient strength to withstand shipping and dropping, without breaking.
- the invention includes a process for making a briquetted detergent tablet.
- Tablets or briquettes produced by compacting beads or granules of detergents have been used as pre-measured detergents and have been found especially useful in laundry applications. With such products it is important that the composition should be completely water soluble or dispersible, so that no undissolved constituents of the detergent composition will remain adhering to the washed material-s. Also, even when the entire composition is completely Water soluble, problems sometimes arise due to the comparatively slow rate of solubility of tablet particles which become entrapped in the textiles being used. Sometimes, detergent particles held closely against laundry being washed cause objectionable discoloration thereof.
- lightly compacted detergent briquettes To overcome poor surface properties of lightly compacted detergent briquettes, they have been subjected to treatments after pressing. Water has been applied to form a more continuous surface film, to harden and strengthen the briquette at its surface and to prevent undesirable chalking and to increase the briquette strength. Film-forming organic polymers have been employed to coat the lightly compacted detergent briquette. Solutions of silicates have been applied to the particles of synthetic detergent composition before compacting and particles have been pro-moistened, before pressing into final shape.
- a detergent tablet of desired shape is made by producing a particulate detergent composition comprising 2 to 20% of a water soluble, non-cationic, synthetic organic detergent, 20 to 50% of a water soluble metal silicate of metal oxide to silica ratio between about 0.3 and 1, 20 to 50% of a water soluble polyphosphate salt and containing less than 13% of water, adding 2 to 35% water to the particulate detergent, to raise the moisture content thereof to 15 to 35%, continuously moving and circulating the moistened detergent composition particles, whereby the moisture is substantially uniformly distributed throughout the mass of said particles, the polyphosphate is substantially hydrated and speed of solution of the alkali metal silicate is increased, 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.
- a detergent tablet such as may be produced by the foregoing method, which comprises 2 to 20% of a water soluble non-cationic synthetic organic detergent, 20 to 50% of a water soluble metal silicate of metal oxide to silica ratio between about 0.3 to I, 20 to 50% of a water soluble polyphosphate salt and 15 to 35% of water, the tablet being comprised of particles of such composition, lightly held to one another, in which the po'lyphosphate is substantially hydrated and the silicate is readily soluble in water.
- a briquette is readily disintegrated in wash water, dissolves completely and may be shipped without fear of breakage.
- 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 detergent examples include the block copolymers of ethylene oxide and propylene 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.
- the proportion should be within the range of 2 to 20%, preferably 5 to 15% of the detergent briquette.
- 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.
- 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 instead of 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 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 and not less than about 2% of the detergent briquette.
- the water soluble metal silicate is the 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, and still disintegrates rapidly in aqueous media and dissolves completely in a short time.
- the silicates allow making of tablets of the 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 1 are most often used.
- a highly preferred silicate is sodium metasilicate having a Na O1SiO 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.
- 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.
- water in addition to the fourth constituent of the invented briquettes, water, other adjuvants, useful to give the detergent briquettes special desirable properties, may be included.
- additional builders foam enhancers or suppressors, coloring agents, perfumes, 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 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 5 to 15%. 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 from 20 to 50%, preferably 25 to 40% of the briquette. Such percentages of these materials contribute excellent building and detergent properties to the product and complement the silicate to allow the pro duction of a quick dissolving tablet of adequate strength and abrasion resistance. Also, 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 soluble silicate comprises 20 to 50% of the briquette and it 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 pro portion of silicate is 25 to 40%.
- the silicate constitutent 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.
- 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. Fifteen to 35% of water in the invented briquettes will accomplish these results and it is preferred to employ 20 to 30% of water in most of the invented compositions, whereby substantial hydration, e.g., hydration or more, of the polyphosphate takes place.
- Moisture added to the particulate detergent is 2 to 35%, preferably 7 to 30%. 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 1 range, are used.
- a particulate detergent is produced in which the organic detergent, silicate and polyphosphate are present. It is highly preferred that such detergent composition constituents be homogeneously distributed throughout the particles and spray dried detergent heads 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 mix 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, US. Standard Sieve Series, are excellent beads to be converted into briquettes or tablets. During the drying operation most of the water present in the crutcher mix is removed but there may be left in the particles up to about 13% 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 a 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 to 35%, preferably to
- the continuously moving and circulating particles may adhere lightly to a number of other particles, in the course of spraying and circulating them but the circulating movement should be such that large lumps of detergent composition are not produced. Lumping or obectionable aggregation can be minimized by maintaining the detergent bed in continuous motion and keeping it thin enough so that agglomerating or compacting pressures exerted on the lowermost particles are not excessive.
- detergent beads are of an apparent density of about 0.3 to 0.6 gram per cubic centimeter. After moistening, this density may be altered somewhat, usually being decreased, e.g., by as much as 30%. 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 maintains 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 polyphosphates 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 being moistened is kept in continuous motion and the moisture is applied in fine droplet form.
- Mixing, moistening, agglomeration, removal and pressing to cake or tablet form should be conducted continuously and without more than momentary halts, so as to obtain a satisfactory product by a feasible process.
- 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 tablet, which is most often from about to 1 inch thick. Pressures over 100 pounds per square inch should be avoided. Pressing is preferably effected between opposed dies having Teflon Before moistening, the
- the detergent briquettes prepared are of sufficient 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. Surprisingly, the lighter briquettes are even stronger than comparable heavier materials made with less silicate. They are made by a more eificient process and can be produced by tableting and briquetting equipment of conventional design. Due to the elimination of a coating operation, heretofore considered to be necessary and still considered important for other detergent tablet formulations, production rates and efficiency can be increased. Furthermore, all this is accomplished without the necessity for inclusion of comparatively expensive conditioning or adjuvant materials in the detergents.
- the moistening solution may include adjuvant materials not stable to heat, e.g., emulisfied perfumes. Some sodium silicate may be added with that solution.
- 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.
- moisture tight wrappers e.g., sleeves of polyethylene film
- Products made according to this invention have been subjected to severe testing and usually 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, they 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.
- All proportions are by weight, unless otherwise indicated.
- Example I Ingredient: Parts Nonyl phenol polyoxyethylene ethanol, avering about 9.5 oxyethylene groups, per molecule 9.4 Sodium tripolyphosphate, anhydrous 28.9
- the above formula describes the composition of a final detergent briquette or tablet which was found to be of excellent cleaning power, quickly disintegrable in wash water and extremely strong and resistant to breakage and abrasion.
- the briquettes were made by mixing together in a crutcher the nonionic detergent, sodium tripolyphosphate, sodium silicate and coloring agents, producing a uniform aqueous slurry therefrom of approximately 0% solids content and spray drying this slurry in a drying gas in a conventional spray tower.
- the product resulting was of conventional head shape and was classified and sieved to be within the 8 to 100 mesh range.
- the moisture content of the powder produced was approximately 8% thereof.
- the spray dried detergent beads were tumbled continuously in a suitable mixer, e.g., a tilted drum mix-er, and moisture was sprayed onto the beads in fine droplet form so as to uniformly moisten them, up to about 28% water content.
- the perfume was sprayed onto the beads shortly before moistening. After continued agitation to promote an even distribution of moisture, it was found that the bulk density of the product had been decreased, from about 0.4 to 0.3. Tablets were made from this lower density product by pressing 42 grams thereof, into a tablet A3 of an inch thick and 2 /2 inches in diameter.
- the press employed was set with a fixed stop so as to produce consistently the same thickness of tablet.
- the pressing pressure effectively transmitted to the tablet was within the range of about 3 to 25 pounds per square inch.
- the finished tablets were sufficiently hard to be commercially acceptable and yet it was found that they disintegrate in water, whether hot or cold, within 30 seconds, even when not agitated. Some of the tablets broke apart in as little as seconds. The unusually rapid disintegration and accompanying dissolution could be attributable at least in part to the quick removal of dissolving tablet material, as it descended from the floating remaining tablet portion. The tablets did not fragment into lumps in the wash water but dissolved quickly and in a regular manner. When dropped from a height of 5 feet, repeatedly, the tablets did not break. In the washing machine, it was found that experimentally soiled fabrics could be laundered effectively with these tablets and could be cleaned and whitened as well with a lesser weight of the lighter tablet, as compared to commercial tablets now on the market. Also, the present tablets laundered as well as amounts of heavier duty commercial synthetic detergents which contained higher proportions of organic detergent and sodium tripolyphosphate.
- Detergent tablets of the above formulas were made by essentially the same method as that described in Example I.
- the tablets made were substantially in the shape of flat cylinders /8 inch thick and 2 /2 inches in diameter and weighed from 37 to 46 grams each, passed tests of disintegration rates (in water), strength (resistance to fracture on dropping) and abrasion resistance. These products are of excellent cleaning and whitening powers.
- the tablets could be repeatedly dropped from heights of 1 to 4 feet without breaking. They distintegrated in water in from 10 to 30 seconds each. They were not readily abraded when packed together in sleeve wraps of plastic film and subjected to shaking. In all respects mentioned, the products were especially satisfactory for the laundering applications for which they are intended.
- a tablet of the above formula was prepared substantially by the method of Example I.
- the moistened particles were screened to be between 4 and 40 mesh. After pressing at low pressure, they were moistened with water over their surfaces and the added water, about 3% of the :briquette, was dried off.
- the product resulting was tested and found to be completely soluble in water (with the exception of insignificant proportions of pigment and inerts, which were dispersible), quickly disintegrable (10 to 30 seconds) and resistant to breakage, withstanding crushing forces of 20 to 30 pounds applied 12 hours after manufacture.
- the composition was a satisfactory laundry detergent.
- a useful tablet of this formula can also be made without moistening of the pressed briquette but it is preferred to produce a high strength tablet by noistening with about 25% of water, which is dried o
- the invention has been described with reference to several examples thereof. It is not to be limited thereto and its scope is determined by the claims and processes and products equivalent to those claimed.
- a process for manufacturing a detergent tablet which comprises producing a particulate detergent composition comprising 2 to 20% of a water-soluble synthetic organic detergent selected from the group consisting of sulfated and sulfonated anionic detergents and water-soluble nonionic detergents containing both 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, 20 to 50% of a water-soluble alkali metal polyphosphate, 20 to 50% of a water-soluble alkali metal silicate having a metal oxide to silica ratio between about 0.3 and 1, moving and circulating a mass of said particulate detergent, adding 2 to 35% water to the moving and circulating particulate detergent to raise the moisture content thereof to 15 to 35% 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 p.s.i. into form retaining tablets which are readily disintegrable in wash water, soluble therein and resistant to
- a process for manufacturing a detergent tablet which comprises producing a particulate detergent composition comprising 5 to of a water-soluble synthetic organic detergent selected from the group consisting of sulfated and sulfonated anionic detergents and water-soluble nonionic detergents containing both 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, to 40% of a water-soluble alkali metal polyphosphate, 25 to 40% of a Water-soluble alkali metal silicate having a metal oxide to silica ratio between about 0.3 and 1 and up to 13% moisture, adding 7 to water to the particulate detergent to raise the moisture content thereof to 20 to 30%, the addition of moisture being elfected while the particles are being continuously moved and circulated, whereby the moisture is substantially uniformly distributed throughout the mass of said particles, the polyphosphate is substantially hydrated and the speed of solution of the soluble alkali metal silicate is increased and lightly compacting the resulting particles at a pressure of 3
- a process for manufacturing a detergent tablet which comprises making an aqueous crutcher mix of a nonionic synthetic organic detergent containing both hydrophilic and hydrophobic portions in the molecule of which at least the hydrophilic portion includes a plurality of lower joined alkylene oxide groups, water-soluble alkali metal polyphosphate, water-soluble alkali metal silicate having a metal oxide to silica ratio between about 0.3 and 1 and water, in such proportions to be convertible after drying, to a tablet containing 2 to 20% nonionic detergent, 20 to 50% water-soluble alkali metal polyphosphate, 20 to 50% water-soluble alkali metal silicate and 15 to water, drying the crutcher mix to particulate form having a moisture content of less than 13%, continuously moving the dried particulate detergent and spraying on to the moving particles 2 to 35% water to raise the moisture content of the particles to 15 to 35% to substantially hydrate the polyphosphate and increase the solubility of the silicate, the addition of moisture being such that it is distributed uniformly throughout the mass of particles,
- 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 water-soluble 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, 20 to 50% of a water-soluble alkali metal polyphosphate, 20 to 50% of a water-soluble alkali metal silicate having a metal oxide to silica ratio of between about 0.3 and 1, and 15 to 35% water, the tablet being in the form of particles compacted at a pressure of 3 to p.s.i. and being readily disintegrable in water and of a strength to resist breakage in shipment.
- a water-soluble synthetic organic detergent selected from the group consisting of sulfated and sulfonated anionic detergents and water-soluble nonionic detergents containing hydrophilic and hydrophobic portions in the molecule of which at least the hydrophil
- a detergent tablet which comprises 5 to 15% of a water-soluble nonionic synthetic organic detergent containing both hydrophilic and hydrophobic portions in the molecule of which at least the hydrophilic portion includes a plurality of lower joined alkylene oxide groups, 25 to 40% of a water-soluble alkali metal polyphosphate selected from the group consisting of tripolyphosphate and pyrophosphate, 25 to 40% of a water-soluble alkali metal silicate having a metal oxide to silica ratio between about 0.3 and 1 and 20 to 30% water, the tablet being in the form of particles compacted at a pressure of 3 to 100 p.s.i. and being readily distintegrable in water and of sufiicient strength to resist breakage in shipment.
- a detergent tablet which comprises 2 to 20% of a higher alkyl phenol poly lower alkoxy alkanol detergent, 20 to 50% of a water-soluble alkali metal tripolyphosphate, 20 to 50% of a water-soluble alkali metal silicate having a metal oxide to silica ratio of about 0.4 to 1 and 15 to 35% water, in the form of particles compacted at a pressure of 3-100 p.s.i. to a tablet which is readily disintegrable in water and of sufficient strength to resist breakage in shipment.
- a detergent tablet which comprises 5 to 15% of a nonyl phenol polyoxyethylene ethanol in which an average number of ethylene oxide groups is between 9 and 10, 25 to 40% of sodium tripolyphosphate, 25 to 40% of sodium silicate having a Na O:SiO- ratio of 122.35 and 20 to 30% water, the water present substantially completely hydrating the polyphosphate and increasing the solubility of the silicate over that of a heat dried silicate in the form of spray dried particles compacted at a pressure of 3 to 100 p.s.i. to a tablet which is readily disintegrable in Water and of sufiicient strength to resist breakage in shipment.
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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 |
---|---|---|---|
BE635589D BE635589A (enrdf_load_html_response) | 1962-07-30 | ||
CA718383A CA718383A (en) | 1962-07-30 | Manufacture of detergent tablets | |
CA718384A CA718384A (en) | 1962-07-30 | Manufacture of detergent tablets | |
NL295937D NL295937A (enrdf_load_html_response) | 1962-07-30 | ||
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 |
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 |
---|---|---|---|
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 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3247123A true US3247123A (en) | 1966-04-19 |
Family
ID=26907784
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US213117A Expired - Lifetime US3247123A (en) | 1962-07-30 | 1962-07-30 | Manufacture of detergent tablets |
US213116A Expired - Lifetime US3247122A (en) | 1962-07-30 | 1962-07-30 | Detergent tablet and process of preparing same |
Family Applications After (1)
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 |
Country Status (13)
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
US3370015A (en) * | 1964-01-30 | 1968-02-20 | Lever Brothers Ltd | Process for preparing detergent compositions |
US3392120A (en) * | 1964-03-19 | 1968-07-09 | Fmc Corp | Dry detergent mixtures |
US3408300A (en) * | 1965-12-13 | 1968-10-29 | Henkel & Cie Gmbh | Stable,alkaline,non-forming cleansing agents |
US3455834A (en) * | 1964-01-22 | 1969-07-15 | Colgate Palmolive Co | Process for production of 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 |
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 |
US4839078A (en) * | 1985-11-21 | 1989-06-13 | Henkel Kommanditgesellschaft Auf Aktien | Detergent tablets of uniform composition for dishwashing machines |
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 |
WO2015040452A1 (en) * | 2013-09-18 | 2015-03-26 | Technion Research And Development Ltd. | Concrete formulations and admixtures therefor |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA795287A (en) * | 1965-03-09 | 1968-09-24 | P. Davis Robert | Detergent tablets |
GB2041966A (en) * | 1977-11-29 | 1980-09-17 | Procter & Gamble | Detergent tablet having a hydrated salt coating and process for preparing the tablet |
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 |
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 US213117A patent/US3247123A/en not_active Expired - Lifetime
- 1962-07-30 US US213116A patent/US3247122A/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 DK DK348663AA patent/DK117972B/da unknown
- 1963-07-22 DE DE19631467564 patent/DE1467564A1/de active Pending
- 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 (18)
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 |
US3370015A (en) * | 1964-01-30 | 1968-02-20 | Lever Brothers Ltd | Process for preparing detergent compositions |
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 |
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 |
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 |
US4839078A (en) * | 1985-11-21 | 1989-06-13 | Henkel Kommanditgesellschaft Auf Aktien | Detergent tablets of uniform composition for dishwashing machines |
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 |
WO2015040452A1 (en) * | 2013-09-18 | 2015-03-26 | Technion Research And Development Ltd. | Concrete formulations and admixtures therefor |
CN105793210A (zh) * | 2013-09-18 | 2016-07-20 | 理工研究与开发公司 | 混凝土配方和其掺入剂 |
CN105793210B (zh) * | 2013-09-18 | 2018-06-12 | 理工研究与开发公司 | 混凝土配方和其掺入剂 |
Also Published As
Publication number | Publication date |
---|---|
GB995940A (en) | 1965-06-23 |
CH439554A (de) | 1967-07-15 |
AU3279063A (en) | 1965-01-14 |
CA718384A (en) | 1965-09-21 |
MY6600098A (en) | 1966-12-31 |
NL295937A (enrdf_load_html_response) | |
DE1467564A1 (de) | 1969-10-09 |
FR1387029A (fr) | 1965-01-29 |
CA718383A (en) | 1965-09-21 |
ES290152A1 (es) | 1963-10-16 |
BE635589A (enrdf_load_html_response) | |
BR6351230D0 (pt) | 1973-08-28 |
US3247122A (en) | 1966-04-19 |
DK117972B (da) | 1970-06-22 |
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