US3743600A - Solid blends of peroxy compounds and phosphate containing detergent bases - Google Patents
Solid blends of peroxy compounds and phosphate containing detergent bases Download PDFInfo
- Publication number
- US3743600A US3743600A US00056636A US3743600DA US3743600A US 3743600 A US3743600 A US 3743600A US 00056636 A US00056636 A US 00056636A US 3743600D A US3743600D A US 3743600DA US 3743600 A US3743600 A US 3743600A
- Authority
- US
- United States
- Prior art keywords
- detergent
- bulk density
- base
- composition
- detergent base
- 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 abstract description 79
- 239000000203 mixture Substances 0.000 title abstract description 69
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 9
- 239000010452 phosphate Substances 0.000 title abstract description 9
- 239000007787 solid Substances 0.000 title abstract description 5
- 125000000864 peroxy group Chemical group O(O*)* 0.000 title description 9
- 239000002245 particle Substances 0.000 abstract description 55
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 abstract description 24
- 239000001301 oxygen Substances 0.000 abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 15
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 abstract description 8
- 239000002585 base Substances 0.000 description 50
- 238000009826 distribution Methods 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 238000005204 segregation Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- -1 peroxy compound Chemical class 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 208000025814 Inflammatory myopathy with abundant macrophages Diseases 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C11D3/39—Organic or inorganic per-compounds
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
Definitions
- a particulate detergent composition comprising phosphate containing detergent base and a solid blend of peroxy compounds comprising inorganic peroxidic compounds selected from the group consisting of percarbonates, perborates in the form of an active oxygen containing material consisting of substantially regular particles of which at least 80% by weight have diameters which vary by not substantially more than 25% from the average mean diameter of the inorganic peroxy compound particles.
- the perborate and percarbonate components manifest the bulk density of 1:3 times that of the detergent base and an average mean particle diameter within 25 of the norm.
- the invention relates to peroxy compounds and particularly to detergent compositions containing peroxy compounds.
- This invention provides a particulate detergent composition
- a particulate detergent composition comprising a major proportion, based on the weight of the detergent composition, of a homogeneous detergent base having a normal size distribution and consisting of substantially regular particles and, distributed therein, a minor proportion, based on the weight of the detergent composition, of an active oxygen containing compound or compounds in the form of an active oxygen containing material consisting of substantially regular particles of which at least 80% by weight have diameters which vary by not substantially more than 25% from the average particle diameter of the material, having a bulk density of from 100% to 300% of that of the detergent base and having an average particle diameter of where X has a value of from 0.4 to 0.7 and when P, B and B are as herein defined.
- P, B and B used herein denote numerical values equal, respectively, to the average particle size of the detergent base in mm. and the bulk density, measured as herein described in g./cc., of the active oxygencontaining material and of the detergent base.
- a normal size distribution we mean a distribution which varies in a continuous manner and peaks at a point intermediate to the minimum and maximum particle size.
- compositions according to the invention must consist of substantially regular shape, we prefer them to be generally spherical.
- diameter of particles herein we mean the diameter as determined by conventional sieve analysis using a nest of sieves.
- Solid detergent compositions which comprise a blend of a minor proportion of a particulate active oxygen-containing compound and a major proportion of a homogeneous particulate material which contains the remaining constituents of the detergent composition (the detergent base) may tend to segregate. It is, however, desirable that the active oxygen containing compound remain distributed throughout the detergent composition. It has been proposed in the past to reduce the tendency of blends to segregate by ensuring that their various constituents have a similar size distribution.
- Active oxygen containing compounds often have a lower rate of solution than the detergent bases conventionally used and particles of a size which corresponds to the largest found in the detergent base may remain undissolved after the remainder of the composition has gone into solution. It may therefore be disadvantageous to attempt to reduce the tendency of such compositions to segregate by matching the particle size distribution of their constituents.
- the detergent compositions provided by the present invention have excellent characteristics in relation to their tendency to segregate, particularly in comparison with similar blends in which the minor proportion has an average particle diameter outside the essential limits set forth above, and also have acceptable rates of solution.
- phosphate containing detergent base having a normal particle size distribution
- a preferred species of phosphated detergent base is that material known by the trade name Deepio marketed by Procter & Gamble, Cincinnati, Ohio, which is a mixture of 34% by weight sodium tripolyphosphate, 7% by Weight sodium silicate, 29% by weight sodium sulphate and minor ingredients, 23% by weight sodium dodecyl benzene sulfonate, the balance of the composition being Water.
- detergent base which may either be cationic, anionic or non-ionic
- phosphate builders may be added to detergents such as alkyl sulphates and alkane sulphonates to increase their detergent effciency as well as their anti-corrosive properties.
- Sodium hydrogen phosphate is claimed to be an efiective builder for a variety of sulfonic and sulfuric ester detergents as described in US. Pat. 2,383,502 to Quimby.
- mixtures of tetrasodium-p-phosphate and acid reacting salts which provide a pH of less than 7, have been used for the same purpose particularly with respect to detergents of the type described in Henderson et al. US. Pat. 2,279,314.
- Other detergent bases, therefore, which contain phosphate ions are particularly useful in the practice of this invention.
- the minor proportion of the detergent composition comprises, substantially solely, one or more active-oxygen containing compounds.
- the preferred active oxygen containing compounds are inorganic peroxidic compounds for example alkali metal peroxidic compounds such as percarbonates, perborates, persulphates, perphosphates and perpyrophosphates.
- the composition according to our invention and particularly in the detergent composition described above, to use a detergent base which has an average particle size of from 0.1 to 1.0 mm.
- the detergent base has a bulk density; measured as herein described, of from 0.2 to 0.6 g./cc.
- the detergent base has an average particle size of from 0.3 to 0.7 and/or a bulk density of from 0.2 to 0.5 g./ cc.
- the active oxygen-containing material is advantageously present in not more than 25%, preferably not more than 20%, by weight of the detergent composition and it advantageously also has a bulk density of from 100% to 270% of that of the detergent base.
- this invention provides a particulate detergent composition comprising at least based on the weight of the detergent composition, of a homogeneous detergent base having a normal size distribution consisting of substantially regular particles having a particle size of from 0.1 to 1.0 mm. in diameter and a bulk density of 0.2 to 0.6 g./cc.
- alkali metal percarbonates or perborates consisting of substantially regular particles of which at least 80% by weight have diameters which vary by not substantially more than 25% from the average particle diameter of the percarbonate or perborate, having a bulk density of from 100% to 270% of that of the detergent base and having an average particle diameter of (2.5PX)(l+B -B mm.
- X has a value of from 0.4 to 0.7
- P, B and E are as herein defined.
- Detergent compositions provided in this last embodiment of the invention show, particularly, a reduced tendency to segregate.
- the detergent base has a bulk density of 0.2 to 0.5 g./ cc. and/ or has an average particle size of from 0.3 to 0.7 mm. in diameter.
- the alkali metal perborate or percarbonate has an average particle diameter expressed in mm. by the general formula referred to above wherein X is a numerical value of from 0.45 to 0.65.
- the invention particularly provides detergent compositions where the detergent base has a bulk density of 0.2 to 0.5 g./cc. and an average particle size of from 0.3 to 0.7 mm. in diameter and the active oxygen containing compound or compounds is or are selected from alkali metal perborates and percarbonates and has or have an average particle diameter expressed in mm. by the general formula referred to above wherein X is a numerical value of from 0.45 to 0.65 and are present in not more than by Weight of the blend.
- detergent compositions which have a degree of segregation of not substantially more than 20
- compositions we prefer those in which the detergent base is that known by the trade name Deepio and the active oxygen containing compound is sodium percarbonate.
- This invention also provides a process for the production of liquid compositions in which the soluble blends provided herein are dissolved and/or processes for the utilization of such compositions particularly cleaning processes for, for instance, textiles which comprise dissolving detergent compositions provided herein in an aqueous liquid and contacting the material to be cleaned with resulting solution, if desired at elevated temperatures, and separating the cleaned material from the solution.
- a truncated cone shaped hopper of stainless steel having a largest internal diameter of 53 mm., a smallest in ternal diameter of 21 mm., an axial height of 58 mm. and provided at its narrow end with a totally opening shutter, is clamped in the axially vertical position and filled with the particulate material until it overflows the top being levelled 01f without compression of the contents.
- a cylindrical cup of stainless steel of internal diameter of 45.2 mm. and of about the same height and of 50 ml. capacity is placed vertically below the hopper, the lower end of the hopper being 65 mm. above the plane of the top of the cup and the cup is then filled to overflowing from the hopper and is levelled 01f without com pression of the contents.
- the apparent specific gravity by free flow is the weight in grams of the contents of the cup divided by 50 in g./ cc.
- FIGS. 1 and 2 represent, in plan and elevation respectively, hopper A which consists of an upper portion 11 which has a square horizontal section having each side 5 cm. long and a lower pyramidal portion 12 the apex of the pyramid being truncated so as to provide a rectangular opening 13, which has sides 2.5 and 0.5 cm. long, in the base of the hopper.
- the vertical distance from the base 111 of the pyramid to the opening 13 is 2.5 cm.
- the opening 13 comprises the hopper discharge means and is totally or partially closable by a shutter (not shown) sliding parallel to its longer sides.
- FIGS. 3 and 4 represent, in elevational and plan view respectively, a further hopper B which is bounded by two identical trapezoidal sides 14 which lie in planes parallel to each other, and two identical rectangular sides 15.
- Each trapezoidal side has a longer parallel side 16 of 20.8 cm. in length, a shorter parallel side 17 of 1.1 cm. in length and an angle between each non-parallel side and the shorter parallel side of
- Each rectangular hopper side measures 3.8 cm. across its shorter sides 18.
- the base 119 of the hopper is open and comprises the hopper discharge means, being totally or partially closable by a shutter (not shown) sliding parallel to the short sides of the rectangular hopper sides.
- FIGS. 5 and 6 represent, in elevation and plan respectively, a rectangular receiving vessel C standing upright in its base 20 which is 1.3 cms. in width.
- the base 20 which has openings 21, 22, 23 and 24 seen in FIG. 6 each of which is 0.9 cm. wide, extends across the whole width of the vessel and is totally or partially closable by means of a shutter (not shown) sliding parallel to the width of the base, and the base and the top of the vessel, which is open, each having along dimension of 28:8 cms.
- the vessel has a vertical height of 25.4 cms.
- Opening 21 has a centre point coinciding with that of the base of the vessel and openings 22, 23 and 24 have respectively, a centre point 3.4 cms., 6.0 cms. and 13.0 cms. from that of opening 21.
- FIGS. 1-6 The apparatus illustrated in FIGS. 1-6 was employed to measure the degree of segregation of detergent blends as described below.
- a thoroughly blended detergent composition comprising 117 g. of a phosphate containing detergent base referred to commercially as Deepio and described below in detail as to specific composition and 13 g. of an active oxygen containing compound such as sodium percarbonate was poured into hopper A, discharge means ⁇ 13 being closed.
- Hopper B was positioned with its closed discharge means 9 lower-most and in the horizontal plane. Hopper A was positioned so that its discharge means 13 lay in the plane of the mouth of hopper B, was symmetrically vertically above the discharged means and so that the long sides of openings 13 and 19 were all parallel, the shutters of each opening in the same direction.
- Discharge means 13 was then partially opened so that the blend ran slowly into hopper B discharge means 19 being closed.
- Hopper B was then positioned over upright receiving vessel C, discharge means 19 coinciding with the plane of the open top of vessel C, having its long sides parallel to those of the top of the receiving vessel and so that,
- Discharge means 19 was then partially opened so as to allow the detergent blend to run slowly into vessel C openings 2-1, 22, 23 and 24 being closed.
- a sample of of the detergent bases used in the examples herein were inserted into the equation set forth in claim 1 herein and the value of X was calculated.
- Detergent Base having a bulk density (Bd) of 0.30 and 5 about 38 cc. of detergent was taken from each of openan average Partlcle S126 (P) of 1ngs 21, 22, 23 and 24 and the percentage of active (2 5P X) (1 B B ti l i f oxygen containing compound in each, based on the total hydrate in mm. such content of all four samples, was determined by (2 30):O 58 chemical means. 10
- composition of each ing an average particle size corresponding to a value of blend and the degree of segregation found are sum- X within those allowed herein are within the invention 30 marised in Table 1 herein.
- blends Nos. 1, invention are complied with. 5-12, -18, -24, 27 and 28 are outside the scope of
- the active oxygen containing material to be used may the invention (they are inserted for comparative purposes be obtained by suitably sieving normally obtainable aconly) and blends 2, 3, 4, 13, 14, 19, and 26 are active oxygen containing material or, if material having a cording to the invention.
- Deepio 74 13 40 limited particle size and bulk density is required, by processes as described in, or analogous to, those described in US. Pat. No. 3,463,618.
- Example 12 of that patent describes the production of sodium carbonate perhydrate having a bulk density of 0.54 g./cc., determined by the same method as described herein, an average particle size of about 0.58 mm. and has a size distribution such that 92.8% by weight of the particles are between 0.353 mm. and 0.801 mm. in diameter. It is apparent from the particle size distribution disclosed that more than 80% by weight of the particles have diameters between 0.42 and 0.75 mm.
- the relevant dimensions of the above described sodium carbonate perhydrate and each 7 being from 100% to 300% of the bulk density of the detergent base and the average particle diameter of the peroxy containing particles in millimeters being equal to wherein X has a value of from 0.4 to 0.7; P is the average particle size of the detergent base in millimeters; B is thebulk density of the peroxy containing particles in g./cc.; and E is the bulk density of the detergent base in g./cc., at least 8.0% by weight of the peroXy containing particles having diameters which vary by not substantially more than 25 of the average particle diameter.
- composition as claimed in claim 1 wherein the peroxy compounds are alkali metal percarbonates or perborates.
- a process for cleaning textile materials comprising dissolving a composition as claimed in claim 1 in an aqueous liquid, contacting a textile material with the resulting solution and separating the material from the solution.
- composition as claimed in claim 2 wherein the detergent base has a bulk density of 0.25 to 0.4.
- a particulate detergent composition consisting essentially of (a) at least 80%, by weight of the composition, of substantially regular particles of phosphated detergent base having an average particle size of from 0.35 to 0.55 mm. in diameter in normal siz distribution and a bulk density of from 0.25 to 0.4 g./ cc. and
- composition as claimed in claim 7 wherein the alkali metal percarbonate or perborate has a bulk density of from to 240% of that of the detergent base.
- composition as claimed in claim 9 wherein the alkali metal percarbonate or perborate has a bulk density of from 100% to 240% of that of the detergent base.
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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)
- Silicon Compounds (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB5039/66A GB1178241A (en) | 1966-02-04 | 1966-02-04 | Solid Blends of Peroxy Compounds. |
Publications (1)
Publication Number | Publication Date |
---|---|
US3743600A true US3743600A (en) | 1973-07-03 |
Family
ID=9788602
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00056636A Expired - Lifetime US3743600A (en) | 1966-02-04 | 1970-07-20 | Solid blends of peroxy compounds and phosphate containing detergent bases |
Country Status (10)
Country | Link |
---|---|
US (1) | US3743600A (en)van) |
AT (1) | AT287882B (en)van) |
BE (1) | BE693293A (en)van) |
CH (1) | CH480433A (en)van) |
DE (1) | DE1617150A1 (en)van) |
DK (1) | DK127073B (en)van) |
ES (1) | ES336338A1 (en)van) |
GB (1) | GB1178241A (en)van) |
NL (1) | NL6701745A (en)van) |
NO (1) | NO120802B (en)van) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USD463067S1 (en) | 2001-05-22 | 2002-09-17 | Reckitt Benckiser N.V. | Diamond shape detergent tablet |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018202012A1 (de) * | 2018-02-08 | 2019-08-08 | Benninghoven Gmbh & Co. Kg | Schüttguttrichter und Schüttgut-Beschickungsanlage mit einem Schüttguttrichter |
-
1966
- 1966-02-04 GB GB5039/66A patent/GB1178241A/en not_active Expired
-
1967
- 1967-01-24 NO NO166550A patent/NO120802B/no unknown
- 1967-01-25 DK DK44867AA patent/DK127073B/da unknown
- 1967-01-27 BE BE693293D patent/BE693293A/xx unknown
- 1967-01-30 CH CH131367A patent/CH480433A/de not_active IP Right Cessation
- 1967-02-01 ES ES336338A patent/ES336338A1/es not_active Expired
- 1967-02-03 NL NL6701745A patent/NL6701745A/xx unknown
- 1967-02-03 AT AT106067A patent/AT287882B/de not_active IP Right Cessation
- 1967-02-03 DE DE19671617150 patent/DE1617150A1/de active Pending
-
1970
- 1970-07-20 US US00056636A patent/US3743600A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USD463067S1 (en) | 2001-05-22 | 2002-09-17 | Reckitt Benckiser N.V. | Diamond shape detergent tablet |
Also Published As
Publication number | Publication date |
---|---|
AT287882B (de) | 1971-02-10 |
BE693293A (en)van) | 1967-07-03 |
ES336338A1 (es) | 1968-04-01 |
CH480433A (de) | 1969-10-31 |
DE1617150A1 (de) | 1971-02-18 |
NO120802B (en)van) | 1970-12-07 |
GB1178241A (en) | 1970-01-21 |
NL6701745A (en)van) | 1967-08-07 |
DK127073B (da) | 1973-09-17 |
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