US3852220A - Isocyanurate-based polyelectrolyte detergent composition - Google Patents

Isocyanurate-based polyelectrolyte detergent composition Download PDF

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US3852220A
US3852220A US00217223A US21722372A US3852220A US 3852220 A US3852220 A US 3852220A US 00217223 A US00217223 A US 00217223A US 21722372 A US21722372 A US 21722372A US 3852220 A US3852220 A US 3852220A
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percent
isocyanurate
sodium
weight
detergent
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US00217223A
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A Kimmel
P Argabright
C Presley
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Marathon Oil Co
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Marathon Oil Co
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Priority to US00217223A priority Critical patent/US3852220A/en
Priority to IT29953/72A priority patent/IT968511B/it
Priority to DE2250021A priority patent/DE2250021C3/de
Priority to GB5344372A priority patent/GB1411405A/en
Priority to JP47124856A priority patent/JPS51124B2/ja
Priority to FR7246190A priority patent/FR2182798B1/fr
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Publication of US3852220A publication Critical patent/US3852220A/en
Assigned to MARATHON OIL COMPANY, AN OH CORP reassignment MARATHON OIL COMPANY, AN OH CORP ASSIGNS THE ENTIRE INTEREST Assignors: MARATHON PETROLEUM COMPANY
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    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to the field of detergent compositions generally classified in Class 252, subclass 99 of the United States Patent Classification System.
  • Polyelectrolytes that is, substances of relatively high molecular weight which are capable of carrying electronic charges, are incorporated in most detergent formulations, e.g., to counteract the effect of water hardness, to reduce redeposition of soil onto the material being cleaned.
  • the principal polyelectroiytes used in commercially available detergents are polyphosphates and these are beneficial both in reducing hard water precipitate and deposition of soil (J. C. Harris, Detergency Evaluation and Testing, Interscience, 1954, page 158).
  • polyphosphates e.g., trisodium phosphate and disodium phosphate
  • condensed phosphates e.g., tetrasodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, and sodium hexametaphosphate.
  • Such polyelectrolytes fall under the more general term builders which is used to apply to any ingredient of its detergent composition which enhances cleaning performance or cleaning economics.
  • Builders generally act by causing emulsification of soil, stabilizing suspensions of solid soil, neutralizing acid soils as well as counteracting the effect of material constituents present in water or other solvent used to prepare the detergent solution.
  • builders include alkali metal carbonate, bicarbonates, borates, silicates, and phosphates, as well as organic builders such as alkali metal or ammonium amino polycarboxylates, e.g., sodium and potassium ethylene diamine tetraacetate, sodiumand potassiumand triethanol ammonium-in-(2-hydroxy ethyl)-nitrilo diacetate and phytic acid salts.
  • compositions for cleaning purposes which contain compounds characterized by containing in a single molecule the following groups:
  • a monovalent organic radical selected from the following: isocyanate (NCO), urethane (--NH- CO R'), urea (NHCONHR'), amino (NH NHR, or NR,'and may or may not contain, in addition to the above, a metal substituted isocyanurate:
  • X a metal, or hydrogen, or quaternary ammonium (which for the purposes of this invention, acts like a metal) or a combination thereof.
  • Particularly preferred are hydrogen, quaternary ammonium, and metals selected from the following groups of the Periodic Table; Ia, Ib, Ila, llb, Illa, lIIb, lVa, IVb, Va, Vb, VIa; including such metals as Li, Na, K, Rb, Cs, Ca, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al Sc, Y, La, and the other rare earths, Ac, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, and Ir.
  • urea (NHCONHR"), amino (Nl-i NHR, or NR R monovalent hydrocarbon or substituted hydrocarbon radical, as discussed below;
  • m average number of trisubstituted isocyanurate rings is a positive integer from 0 to about 400, and most preferably from 0 to about 200,
  • n average number of isocyanuric acid and/or isocyanurate salt groups is a positive integer from 1 to about 10,000, more preferably from 2 to about 1000, and most preferably from 3 to about 100,
  • 2m n 1 average number of divalent R groups and is a positive integer from 2 to about 110,000, more preferably from 3 to about 1,100, and most preferably from 4 to about 140,
  • m 2 average number of A groups and is a positive integer from 2 to about 2,000, more preferably J... mus-v. .uhuaonaa.
  • R and/or R can be substituted with groups that do not interfere in the product's subsequent utility or in its 2 preparation.
  • non-interfering groups are: -NO,, cl, F, Br, I, CN, CO R, COR", -O-R", -SR", NR CONR -SO,R, SO,, SO-, phenyl naphthyl, alkyl, (1-40 carbon atoms), PO R", cyclohexyl, cyclopropyl, polymethylene (e.g., tetramethylene), OCOR",
  • R may be hydrogen, lower alkyl (e.g., ethyl, hexyl), or aryl (e.g., monovalent radicals corresponding to the aryl radicals described in FIG. 2).
  • R shown in FIG. 2 are set forth for purposes of elucidation, not restriction.
  • the values of m and n, described above, are on the basis of the integers which will be used to describe a single molecule.
  • the invention will involve mixtures of molecules of the general form described above.
  • the average value of m for the mixture may be from about 1 to about 350, more preferably from about l to 200, and most preferably from about I to I; and the value of it may be from about 0 to 2,000, more preferably from 0 to 400, and most preferably from 2 to 200.
  • Various formulations and processes of the present invention are useful in the cleaning of a wide variety of materials such as textiles, e.g., cottons, woolens, and synthetics; dishes, e.g., glassware, pottery, china, plastics, and metal utensils; floors and woodwork, e.g., painted surfaces, wallpapered surfaces, plastics and wood paneling, and lighting fixtures; industrial products, e.g., roll formed, extruded, and stamped metals, molded and extruded plastics; maintenance cleaning, e.g., aircraft, railroad rolling stock, building surfaces, and windows.
  • textiles e.g., cottons, woolens, and synthetics
  • dishes e.g., glassware, pottery, china, plastics, and metal utensils
  • floors and woodwork e.g., painted surfaces, wallpapered surfaces, plastics and wood paneling, and lighting fixtures
  • industrial products e.g., roll formed, extruded, and stamped metals, molded
  • FIG. 1 shows the general formula of the polyelectrolytes of the present invention.
  • FIGS. 2 and 3 exemplify some of the possible structures of R groups of the starting materials and products of the present invention, all of which are more fully described in the aforementioned US. patent application Ser. No. 224,904 filed Feb. 9, 1972 and incorporated herein by reference.
  • the starting materials for the polyelectrolytes of the present invention are salts of polyisocyanuric acids produced according to the techniques taught in US. Pat. No. 3,573,259 (issued Mar. 30, 1971), by reacting a metal cyanate and an organic diisocyanate in the presence of an aprotic solvent to form isocyanuratecontaining polyisocyanate metal salts.
  • Reaction Media Water or mixtures of water and an alcohol, ketone, ester, amide, sulfoxide, sulfone, etc. Temperature While not narrowly critical, temperatures in the range from l0 to about 200C. are preferred, with l5l50C. being more preferred, and 20-l 20C. being most preferred. The lower limit is generally the freeezing point of solution and the upper limit is generally the boiling point of the solution at the reaction pressure.
  • reaction can be carried out at pressures of from 0.5 to I00, with 0.6 to 50 being more preferred, and 0.7 to 10 atmospheres being most preferred.
  • the reaction time is dependent of the initial concentration of the starting materials and the temperature.
  • the preferred time is from 0.0l to 4500 hours, more preferred 0.05 to 350 hours, and most preferred from 0.06 to 200 hours.
  • formulations of the present invention will be prepared by substituting the isocyanurate-based polyelectrolytes for all or part of the conventional polyelectrolytes previously employed in detergent fonnulations suited for the particular cleaning purpose.
  • the techniques of the above references and other detergent formulation techniques well known to those skilled in the art, can readily be employed in preparing the new detergent formulations and in optimizing them for maximum cleaning efficiency with minimum injury to the materials being cleaned and minimum toxcity hazard e.g., to children in the case of household-type automatic dishwasher compounds and laundry detergent formulations.
  • the new detergent fonnulations will comprise one or more isocyanurate-based polyelectrolyte, together with one or more materials selected from the following: surfactants, e.g., anionic, nonionic, cationic, phosphates (if not wholly replaced by the isocyanuratebased polyelectrolytes), silicates, carbonates, oxygenreleasing materials, bleaches, optical brighteners, viscosity control agents (used with liquid formulations), solid or liquid diluents, e.g., sodium sulfate, sodium chloride, water, pH buffers, anti-redeposition agents, e.g., carboxymethylcellulose alkali metal salt (CMC) chelating agents, e.g., ethylenediarninetetraacetic acid or its alkali metal salt, e.g., sodium salt, hydrotropes,
  • surfactants e.g., anionic, nonionic, cationic, phosphates (if not wholly replaced
  • lower alkyl aryl sulfonates used for maintaining materials in solution in liquid formulations, amines and other organic compounds which add alkalinity to liquid formulations, e.g. monoethanol amine, diisopropanol amine, morpholine, alkyl alkanolamine, etc.
  • the polyelectrolytes of the present invention are compatible with a wide range of common detergent formulations.
  • the isocyanurate-based polyelectrolytes do not pose any unusual corrosion problems in conjunction with metals commonly used for fabricating of cleaning equipment.
  • Formulations-Laundry Typical laundry formulations are exemplified by detergent formulations numbered 2-6 in Table 5 of Example XXl. In terms of weight percent, these various ingredients typically comprise the following preferred, more preferred, and most preferred ranges: surfactant, e.g., alkyl aryl sulfonate, dodecyl benzene sulfonate or alkyl sulfate, preferably 2-70, more preferably 10-60,
  • surfactant e.g., alkyl aryl sulfonate, dodecyl benzene sulfonate or alkyl sulfate, preferably 2-70, more preferably 10-60
  • phosphate builder e.g., sodium tripolyphosphate, sodium tetrapyrophosphate or trisodium phosphate, preferably -70, more preferably 0-60, and most preferably 0-50 percent
  • silicate builder e.g., sodium metasilicate, sodium ortho silicate or sodium sesquisilicate, preferably 0-40, more preferably -30, and most preferably 15-25 percent
  • antiredeposition agents e.g., sodium carboxymethylcellulose, or starch, preferably 0-15, more preferably 0-10, and most preferably 2-8 percent
  • carbonate or other builder e.g., sodium carbonate borax or sodium sesquicarbonate, preferably 0-40, more preferably 0-35, and most preferably -30 percent
  • citrate or other sequesterate e.g., sodium citrate, sodium tartrate, or sodium gluconate, preferably 0-30, more preferably 0-20, and most perferably 5-15
  • Formulations-Automatic Dishwasher Detergents A variety of automatic dishwasher detergents of the present invention are exemplified by fonnulations numbered 2-3 and 5-6 of Table 6 of Example XXII.
  • these various ingredients typically comprise the following preferred, more preferred, and most preferred ranges: phosphate, e,g., sodium tripolyphosphate sodium hexametaphosphate or trisodium phosphate, preferably 0-70, more preferably 0-60, and most preferably 0-50 percent; silicate, e.g., sodium metasilicate, sodium orthosilicate or sodium sesquisilicate, preferably 0-40, more preferably 5-30, and most preferably -25 percent; carbonate or other builder, e.g., sodium carbonate or sodium sesquicarbonate, preferably 0-40, more preferably 0-35, and most preferably 10-30 percent; surfactant, e.g., Triton CF 10, Triton CF 52, or Plurafax RA43, preferably 0-10, more preferably 0-6, and most preferably 2-5 percent; bleach, e.g., chlorine bleach, AC1 66 or Chlorinated Trisodium Phosphate, preferably
  • EXAMPLE 1 Six gallons of anhydrous (less than about 200 ppm water) dimethylforrnamide (DMF) are charged to a 10- gallon, glass-lined reactor manufactured by the Pfaudler Company. 936 grams (11.55 moles) of potassium cyanate (KOCN) hammemiilled to pass through 325 mesh are added. The mixture is heated to 165-l F. (C.) while stirring to maintain good mixing. 1,726 milliliters 12.02 moles) of tolylene diisocyanate (TDl) manufactured by Mobay Chemical Company and designated Grade A /20 mixture is added to the reactor at a rate of approximately 27 milliliters per minute, requiring about 64 minutes total for the TDl addition.
  • KOCN potassium cyanate
  • TDl tolylene diisocyanate
  • Example II The apparatus and starting materials of Example 1 are manipulated as described in Example 1, except that the potassium cyanate (KOCN) used in the reaction is crushed (approximately 200 mesh) rather than hammerrnilled. Specific results are shown in Table 1.
  • KOCN potassium cyanate
  • Example 1 The apparatus and starting materials of Example 1 are manipulated as described in Example 1, except that the TDl addition rate is doubled and the stoichiometric quantity of DMF solvent is reduced by approximately 50 percent. Specific results are shown in Table 1.
  • Example IV The apparatus and starting materials of Example 1 are manipulated as described in Example 1, except that the TDl addition rate is doubled. Specific results are shown in Table 1.
  • Example V The apparatus and starting materials of Example I are manipulated as described in Example 1, except that the TD] addition rate is reduced by one-half. Specific results are shown in Table 1.
  • Example VI The apparatus and starting materials of Example 1 are manipulated as described in Example 1, except that the TD] addition rate is reduced to 40 percent of the original rate, the stoichiometric ratio of dimethylforrnamide solvent is reduced by a factor of one-half, and crushed KOCN is used. Specific results are shown in Table 1.
  • Example VII The apparatus and starting materials of Example 1 are manipulated as described in Example 1, except that the 7 TDI addition rate is reduced by a factor one-half and crushed KOCN is used. Specific results are shown in Table l.
  • EXAMPLE XVIII Compatibility with Inorganic Materials
  • a series of dry mixes is prepared with inorganic detergent builders and the polyelectrolyte in ratios of 95:5, :10, 80:20 and 50:50. Additional inorganic materials and some inorganic salts of organic acids are also prepared at the 90:10 ratio. From these mixes a 1% aqueous solution is prepared and observed for compatibility. If the solutions remain clear for 24 hours, the combination is rated as compatible. If a cloudy solution results and remains cloudy for 24 hours, the mixture is considered incompatible. Table 2 lists the inorganic materials and the results of these experiments.
  • Table 3 and mild steel were partially submerged in a 10 percent solution of polyelectrolyte. At the end of 5 days immersion, weight loss is determined and the specimens examined for liquid phase, vapor phase, and liquid vapor line corrosion. The results of this study are presented in Table 4.
  • Laundry Detergent Formulation and Evaluation A series of laundry detergents are prepared and their washing efficiency is determined in the Tergetometer.
  • the basic formula for the test detergent is that of a major product now being marketed. This product is modified to provide both phosphate and nonphosphate 0 detergents with and without polyelectrolyte. The exact product formula is shown in Table 5.
  • the soil redeposition on clean cloth is calculated as a redeposition index from the following formula:
  • the splash washer is a plastic cylinder 5 in. in diameter, 8% in. long, sealed at the bottom with an outlet in the center for draining.
  • An inlet is located on the side l b in. from the bottom.
  • a removable copper ring with six clips for holding test specimens rests on three screws 3 in. from the top.
  • Test Specimen Preparation A Pretreatment of Slides Wash 18 microscope slides (3 in. X 1 in.) in soapy water, rinse and blot dry, free of spots. Twelve for soiling and six left clean.
  • Soil Composition and Preparation Black oatmeal soil The formula, mixing and application instructions for the black oatmeal spray mixture that is used as soil load on the slides are as follows: Weigh: 65.2 g Quaker Oatmeal (Old Fashioned) 344.3 g water Add: 7% teaspoon salt while cooking over a low fire. Stir occasionally while cooking to prevent sticking. Weigh: 150 g cooked oatmeal, put in Waring Blender and stir while slowly adding 150 ml water. Weigh: 10 g India Ink and add to Waring Blender. Continue mixing until uniform. Remove mixture from blender and refrigerate for approximately 16 hr.
  • a. Cleaning is calculated for each soiled slide. The average of the 12 slides is the test result. 100% is optimum.
  • Redeposition index is calculated for each clean slide. The average of the six is the test result. A redeposition index of 1.00 is optimum.
  • An improved detergent composition consisting essentially of at least about 2 to about 70 weight percent of a surfactant and about 2 to about weight percent of an isocyanurate-based polyelectrolyte, wherein said isocyanurate-based polyelectrolyte has the following chemical structure:
  • R divalent hydrocarbon or substituted hydrocarbon radical and contains about 2 to about 30 carbon atoms selected from the groups of FIGS. 2 and 3
  • a monovalent radical selected from the group consisting of: Li, Na, K, Rb, Cs, Ca, Ag. Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Ac, Ga, ln, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, lr, hydrogen and quaternary ammonium groups,
  • A a monovalent organic radical
  • n average number of isocyanuric acid and/or isocyanurate salt groups is a positive integer from .1 to about 10,000
  • m 2 average number of A groups and is a positive integer from 2 to about 2,000
  • X is a monovalent radical from the group consisting of alkali metal salts and quaternary ammonium groups wherein R contains from about 2 to about 18 carbon atoms and wherein R contains from about 1 to about 20 carbon atoms.
  • compositions comprising isocyanuratebased polyelectrolytes consisting essentially of of from about 2 to about 20 weight percent of said isocyanurate-based polyelectrolytes, together with at least one other detergent ingredient comprising from about 2 to about weight percent of surfactant, about 0 to about 70 weight percent of phhosphate builder, 0 to about 40 weight percent of silicate builder, have the following chemical structure:
  • X a monovalent radical selected from the group consisting of: Li, Na, K, Rb, Cs, Ca, Ag, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, H, Al, Ac, Ga, ln, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, lr, hydrogen and quaternary ammonium groups,
  • A a monovalent organic radical
  • n average number of isocyanuric acid and/or isocyanurate salt groups, and is a positive integer from 1 to about 10,000
  • m 2 average number of A groups and is a positive integer from 2 to about 2,000
  • composition according to claim 3 wherein the sequestering agent comprises 0 to about 20 percent by weight citrate based on the total weight of the formulation.
  • composition according to claim 4 wherein the sesquestering agent comprises from about 5 to about 15 percent sodium citrate based on the weight of the total formulation.
  • sequestrate comprises from about 5 to about l5 percent based on the weight of the total formulation, and is selected from the group consisting of sodium citrate, sodium tartrate, or sodium gluconate.

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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)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US00217223A 1972-01-12 1972-01-12 Isocyanurate-based polyelectrolyte detergent composition Expired - Lifetime US3852220A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US00217223A US3852220A (en) 1972-01-12 1972-01-12 Isocyanurate-based polyelectrolyte detergent composition
IT29953/72A IT968511B (it) 1972-01-12 1972-09-30 Composizioni detergenti di poli elettroliti a base di isocianurati
DE2250021A DE2250021C3 (de) 1972-01-12 1972-10-09 Reinigungsmittel
GB5344372A GB1411405A (en) 1972-01-12 1972-11-20 Detergent compositions
JP47124856A JPS51124B2 (hu) 1972-01-12 1972-12-14
FR7246190A FR2182798B1 (hu) 1972-01-12 1972-12-26

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JP (1) JPS51124B2 (hu)
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FR (1) FR2182798B1 (hu)
GB (1) GB1411405A (hu)
IT (1) IT968511B (hu)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4039485A (en) * 1973-11-02 1977-08-02 Marathon Oil Company Ion exchange of metals from aqueous solutions using compositions of synthetic resins reacted with polyisocyanurate salts
US4128537A (en) * 1977-07-27 1978-12-05 Ici Americas Inc. Process for preparing ethylenically unsaturated isocyanurates
US4195146A (en) * 1977-07-27 1980-03-25 Ici Americas Inc. Esters of carboxy amino phenyl isocyanurates and vinylidene carbonyl oxy alkanols
US4283535A (en) * 1978-05-13 1981-08-11 Chemische Werke Huls Ag Method for the production of 2,4,6-triketohexahydrotriazines
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US5332580A (en) * 1981-10-27 1994-07-26 Union Oil Company Of California Fumigation method employing an aqueous solution comprising a hexametaphosphate, a thiocarbonate, and a sulfide
US5360782A (en) * 1981-10-27 1994-11-01 Union Oil Company Of California Aqueous solution comprising a thiocarbonate, a sulfide, and an ammoniacal compound
US5374369A (en) * 1993-10-14 1994-12-20 Lever Brothers Company, Division Of Conopco, Inc. Silver anti-tarnishing detergent composition
US5514588A (en) * 1994-12-13 1996-05-07 Exxon Research And Engineering Company Surfactant-nutrients for bioremediation of hydrocarbon contaminated soils and water
US5786317A (en) * 1996-11-22 1998-07-28 Townsend; Clint E. Stain removal compositions for carpets
US20060100124A1 (en) * 2004-11-10 2006-05-11 Rhodia, Inc. Antibacterial composition and methods thereof
US10189798B2 (en) 2014-10-01 2019-01-29 Medical Technology Research Inc Antimicrobial compounds, methods of making the same and articles comprising them

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5830955U (ja) * 1981-08-18 1983-02-28 株式会社　セコ−技研 エジエクト機構

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573259A (en) * 1968-03-22 1971-03-30 Marathon Oil Co Process for the preparation of isocyanurate-containing polyisocyanate salts
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces
US3707503A (en) * 1970-11-25 1972-12-26 Lever Brothers Ltd Stabilized liquid detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573259A (en) * 1968-03-22 1971-03-30 Marathon Oil Co Process for the preparation of isocyanurate-containing polyisocyanate salts
US3692684A (en) * 1969-10-01 1972-09-19 Valter Sven Erwin Hentschel Detergent
US3700599A (en) * 1970-09-25 1972-10-24 Economics Lab Composition for mechanically cleaning hard surfaces
US3707503A (en) * 1970-11-25 1972-12-26 Lever Brothers Ltd Stabilized liquid detergent composition

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4039485A (en) * 1973-11-02 1977-08-02 Marathon Oil Company Ion exchange of metals from aqueous solutions using compositions of synthetic resins reacted with polyisocyanurate salts
US4128537A (en) * 1977-07-27 1978-12-05 Ici Americas Inc. Process for preparing ethylenically unsaturated isocyanurates
US4195146A (en) * 1977-07-27 1980-03-25 Ici Americas Inc. Esters of carboxy amino phenyl isocyanurates and vinylidene carbonyl oxy alkanols
US4283535A (en) * 1978-05-13 1981-08-11 Chemische Werke Huls Ag Method for the production of 2,4,6-triketohexahydrotriazines
US5360782A (en) * 1981-10-27 1994-11-01 Union Oil Company Of California Aqueous solution comprising a thiocarbonate, a sulfide, and an ammoniacal compound
US5332580A (en) * 1981-10-27 1994-07-26 Union Oil Company Of California Fumigation method employing an aqueous solution comprising a hexametaphosphate, a thiocarbonate, and a sulfide
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US5374369A (en) * 1993-10-14 1994-12-20 Lever Brothers Company, Division Of Conopco, Inc. Silver anti-tarnishing detergent composition
US5514588A (en) * 1994-12-13 1996-05-07 Exxon Research And Engineering Company Surfactant-nutrients for bioremediation of hydrocarbon contaminated soils and water
US5786317A (en) * 1996-11-22 1998-07-28 Townsend; Clint E. Stain removal compositions for carpets
US20060100124A1 (en) * 2004-11-10 2006-05-11 Rhodia, Inc. Antibacterial composition and methods thereof
US7354888B2 (en) * 2004-11-10 2008-04-08 Danisco A/S Antibacterial composition and methods thereof comprising a ternary builder mixture
US10189798B2 (en) 2014-10-01 2019-01-29 Medical Technology Research Inc Antimicrobial compounds, methods of making the same and articles comprising them

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DE2250021C3 (de) 1975-06-12
DE2250021B2 (hu) 1974-10-24
DE2250021A1 (de) 1973-07-26
GB1411405A (en) 1975-10-22
FR2182798B1 (hu) 1976-04-23
JPS51124B2 (hu) 1976-01-06
JPS4879212A (hu) 1973-10-24
IT968511B (it) 1974-03-20
FR2182798A1 (hu) 1973-12-14

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