Isocyanurate-based Polyelectrolyte Detergent Composition

Abstract

Detergent formulations containing isocyanurate-based polyelectrolytes in conjunction with surfactants and other conventional detergent formulation ingredients. The formulations are useful for cleaning operations, e.g., laundering and dishwashing.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

U.S. patent application Ser. No. 224,904, now allowed describes isocyanurate-based compositions suitable as polyelectrolytes in the present invention.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the field of detergent compositions generally classified in Class 252, subclass 99 of the United States Patent Classification System.

2. Description of the Prior Art

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 polyelectrolytes 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). Among the useful polyphosphates are orthophosphates, e.g., trisodium phosphate and disodium phosphate, condensed phosphates, e.g., tetrasodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate, and sodium hexametaphosphate. (See Chap. 3, Davidsohn and Milwidsky, Synthetic Detergents (1968).) 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. In addition to polyphosphates, 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, sodium- and potassium- and triethanol ammonium-in-(2-hydroxy ethyl)-nitrilo diacetate and phytic acid salts. The wide range of surfactants and other ingredients useful in detergent formulations is discussed in the above-mentioned text and also in Niven, Industrial Detergency (Reinhold, 1955), McCutcheon's Detergents and Emulsifiers Annual (Allured Publishing Corp., 1970 and other years), Sittig, Practical Detergent Manufacture (Noyes Development Corp., 1968, McCutcheon's Patent Review on Soaps, Detergents, and Emulsifiers (1966), and in the literature references cited therein.

The popularly used phosphates have been found in recent years to raise difficulty in pollution by way of eutrophication of rivers and lakes. Various replacements for phosphates polyelectrolytes have been suggested, e.g., nirilotriacetic acid (NTA), (see October 1971 Consumer Reports, page 592-594.) However, some of the non-phosphate detergents, while avoiding eutrophication problems, have posed serious problems of consumers safety. (See April 28, 1971, Chemical Week, pages 10-12.) The polyelectrolytes of the present invention offer a new approach to these problems.

SUMMARY OF THE INVENTION

General Statement of the Invention

The present invention provides new processes and compositions for cleaning purposes which contain compounds characterized by containing in a single molecule the following groups: ##SPC1##

and at least one group selected from the class consisting of: a monovalent organic radical selected from the following: isocyanate (--NCO), urethane (--NHCO.sub.2 R'), urea (--NHCONHR'), amino (--NH.sub.2), --NHR', or --NR.sub.2 ' and may or may not contain, in addition to the above, a metal substituted isocyanurate: ##SPC2##

The compounds of the present invention have the general structure shown in FIG. 1;

where:

R = divalent hydrocarbon or substituted hydrocarbon radical, as described below and exemplified in FIGS. 2 and 3;

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, IIa, IIb, IIIa, IIIb, IVa, 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.

A = a monovalent organic radical selected from the following:

isocyanate (--NCO), urethane (--NHCO.sub.2 R'), urea (--NHCONHR"), amino (--NH.sub.2, --NHR', or --NR.sub.2 ');

R' = monovalent hydrocarbon or substituted hydrocarbon radical, as discussed below;

m = average number of trisubstituted isocyanurate rings and 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, and 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 from 2 to about 400, and most preferably from 2 to about 200;

and wherein there are no N-to-N bonds, no A-to-N bonds, no A-to-A bonds, and no R-to-R bonds.

R preferably contains 2 to 40, more preferably 2 to 30, and most preferably 2 to 18 carbon atoms.

R' preferably contains 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbons, for example --CH.sub.3, --C.sub.2 H.sub.5, --C.sub.3 H.sub.7, i--C.sub.3 H.sub.7, ##SPC3##

R and/or R' can be substituted with groups that do not interfere in the product's subsequent utility or in its preparation. Examples of such non-interfering groups are: --NO.sub.2, cl, F, Br, I, CN, --CO.sub.2 R", --CO--R", --O--R", --SR", NR.sub.2 " --CONR.sub.2 ", --SO.sub.3 R, --SO.sub.2 --, --SO--, phenyl naphthyl, alkyl, (1-40 carbon atoms), PO.sub.3 R", cyclohexyl, cyclopropyl, polymethylene (e.g., tetramethylene), --OCOR", ##SPC4##

etc. where 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). The examples or R (shown in FIG. 2) are set forth for purposes of elucidation, not restriction.

It will be recognized that the values of m and n, described above, are on the basis of the integers which will be used to describe a single molecule. In actual practice, the invention will involve mixtures of molecules of the general form described above. Thus, the average value of m for the mixture may be from about 1 to about 350, more preferably from about 1 to 200, and most preferably from about 1 to 100; and the value of n may be from about 0 to 2,000, more preferably from 0 to 400, and most preferably from 2 to 200.

Utility of the Invention

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.

BRIEF DESCRIPTION OF THE DRAWINGS

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 U.S. patent application Ser. No. 224,904 filed Feb. 9, 1972 and incorporated herein by reference.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Starting Materials

The starting materials for the polyelectrolytes of the present invention are salts of polyisocyanuric acids produced according to the techniques taught in U.S. 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 isocyanurate-containing 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 10.degree. to about 200.degree.C. are preferred, with 15.degree.-150.degree.C. being more preferred, and 20.degree.-120.degree.C. 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.

Pressure

While not narrowly critical, the reaction can be carried out at pressures of from 0.5 to 100, with 0.6 to 50 being more preferred, and 0.7 to 10 atmospheres being most preferred.

Time

The reaction time, of course, is dependent of the initial concentration of the starting materials and the temperature. The preferred time is from 0.01 to 4500 hours, more preferred 0.05 to 350 hours, and most preferred from 0.06 to 200 hours.

Formulations -- General

In general, the 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 formulations 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.

In general, the new detergent formulations 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 isocyanurate-based polyelectrolytes), silicates, carbonates, oxygen-releasing 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., ethylenediaminetetraacetic acid or its alkali metal salt, e.g., sodium salt, hydrotropes, e.g., 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.

As shown by Examples XVIII and XIX, the polyelectrolytes of the present invention are compatible with a wide range of common detergent formulations. As shown by Example XX, 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 XXI. 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, and most preferably 30-50 percent; phosphate builder, e.g., sodium tripolyphosphate, sodium tetrapyrophosphate or trisodium phosphate, preferably 0-70, 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 5-30, 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 10-30 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 percent; together with one or more isocyanurate-based polyelectrolytes totaling preferably 2- 20 percent, more preferably 3-15 percent, and most preferably 4-12 percent.

Obviously, a wide variety of other ingredients can be added to adapt such formulations to particular laundry applications.

Formulations-Automatic Dishwasher Detergents

A variety of automatic dishwasher detergents of the present invention are exemplified by formulations numbered 2-3 and 5-6 of Table 6 of Example XXII.

In terms of weight percent, 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 15-25 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, "ACl 66" or Chlorinated Trisodium Phosphate, preferably 0-15, more preferably 0-7, and most preferably 0-2 percent; together with one or more isocyanurate-based polyelectrolytes totaling preferably 2-20 percent, more preferably 3-15 percent, and most preferably 4-12 percent. Obviously, a wide variety of other ingredients can be added to adapt such formulations to particular cleaning applications.

EXAMPLES

EXAMPLE I

Six gallons of anhydrous (less than about 200 ppm water) dimethylformamide (DMF) are charged to a 10-gallon, glass-lined reactor manufactured by the Pfaudler Company. 936 grams (11.55 moles) of potassium cyanate (KOCN) hammermilled to pass through 325 mesh are added. The mixture is heated to 165.degree.-170.degree.F. (75.degree.C.) while stirring to maintain good mixing. 1,726 milliliters (12.02 moles) of tolylene diisocyanate (TDI) manufactured by Mobay Chemical Company and designated "Grade A 80/20 mixture" is added to the reactor at a rate of approximately 27 milliliters per minute, requiring about 64 minutes total for the TDI addition. Ten minutes after addition of the TDI is completed, 3,000 milliliters of methanol is added to dilute the reaction mixture and stop the reaction. The temperature is then maintained at 165.degree.-170.degree.F. (75.degree.C.) with stirring for three additional hours. Thereafter, the reaction mixture is cooled to room temperature and filtered (centrifugation may be used instead). The solids are then dried at 175.degree.F. (80.degree.C.) and the resulting product is analyzed. Specific results of analysis and a summary of the stoichiometric ratios, reaction temperature, and other reaction conditions are shown in Table 1.

EXAMPLE II

The apparatus and starting materials of Example I are manipulated as described in Example I, except that the potassium cyanate (KOCN) used in the reaction is crushed (approximately 200 mesh) rather than hammermilled. Specific results are shown in Table 1.

EXAMPLE III

The apparatus and starting materials of Example I are manipulated as described in Example I, except that the TDI 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 I are manipulated as described in Example I, except that the TDI 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 I, except that the TDI addition rate is reduced by one-half. Specific results are shown in Table 1.

EXAMPLE VI

The apparatus and starting materials of Example I are manipulated as described in Example I, except that the TDI addition rate is reduced to 40 percent of the original rate, the stoichiometric ratio of dimethylformamide 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 I are manipulated as described in Example I, except that the TDI addition rate is reduced by a factor one-half and crushed KOCN is used. Specific results are shown in Table 1.

EXAMPLE VIII

The apparatus and starting materials of Example I are manipulated as described in Example I, except that the TDI addition rate is reduced by a factor of one-half and crushed KOCN is used. Specific results are shown in Table 1.

EXAMPLES IX-XVI

Fifty-eight gallons of anhydrous (less than 200 ppm water) dimethylformamide (DMF) are charged to a 100-gallon, glass-lined reactor manufactured by the Pfaudler Company. Twenty and six-tenths pounds of potassium cyanate (KOCN), crushed to pass a 200 mesh screen, are added. The mixture is heated to 165.degree.-170.degree.F. (75.degree.C.) while stirring to maintain good mixing. A total of 46.4 pounds of tolylene diisocyanate (TDI) is added to the reactor at a rate of approximately 0.008 mole of TDI per minute per mole of KOCN in the reactor. This addition requires a total of approximately 132 minutes. Ten minutes after the addition of TDI is complete, 63.0 pounds of methanol is added to dilute the reaction mixture and stop the reaction. The temperature is then maintained at 165.degree.-170.degree.F. (75.degree.C.) with stirring for three additional hours. Thereafter, the reaction mixture is cooled to room temperature and centrifuged. The solids are dried at 175.degree.F. (80.degree.C.) and the resulting product is analyzed. Specific results of analysis and the specific stoichiometric ratios, temperatures, and other reaction conditions are shown in Table 1. ##SPC5##

EXAMPLE XVII

Acute Oral Toxicity, Skin and Eye Irritation

When the product of Example XIV, above, is conventionally tested with rats and mice it is classified as relatively non-toxic because the compound is found not to be toxic after single dosages at a level of 4 gr. per kilogram of body weight and no adverse effects are noted during a 14 day observation period after such dosages. Skin and eye irritation is found to be of a very low order.

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, 90:10, 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.

From the data obtained from this study, it is evident that the isocyanurate-based polyelectrolyte is compatible with all the common inorganic detergent builders studied.

Table 2 __________________________________________________________________________ COMPATIBILITY OF POLYELECTROLYTE OF EXAMPLE I WITH COMMON DETERGENT BUILDER (INORGANIC SALTS) 1% SOLUTION OR MIX IN WATER Ratio Polyelectrolyte to Builder Salt Builder Salt 5:95 10:90 20:80 50:50 __________________________________________________________________________ Sodium Metal Silicate C C C C Sodium Sesquisilica NS C NS NS Sodium Ortho Silicate NS C NS NS Trisodium Phosphate C C C C Sodium Tripoly Phosphate C C C C Tetra Sodium Pyro Phosphate C C C C Borax NS C NS NS Sodium Carbonate C C C C Sodium Sesquicarbonate C C C C Sodiumn Sulfate C C C C Sodium Citrate NS C NS NS Sodium Gluconate NS C NS NS Sodium Hydroxide C C C C __________________________________________________________________________ Note: C = Compatible I = Incompatible NS = Not Studied EXAMPLE XIX

Compatibility with Surfactants

A series of experiments is conducted to determine the compatibility of the polyelectrolyte with the three types of surfactants (anionic, non-ionic and cationic). For these experiments, a 10 percent stock solution of the electrolyte is prepared. Two each of the various surfactants are added in portions of 1 and 3 percent on a weight basis of 50 ml of the stock solution. A clear solution after 24 hr indicates compatibility. A cloudy solution persistent for 24 hr indicates incompatibility. Included with the surfactants are both EDTA and NTA tested at the same levels. Table 3 presents the results of this study.

These experiments show that the isocyanurate-based polyelectolyte is compatible with anionic and nonionic surfactants, EDTA and NTA. It is incompatible with one of the cationic surfactants and compatible with the other. This latter result indicates that when the polyelectrolyte is used with cationic surfactants, a compatibility determination must be conducted.

Table 3 __________________________________________________________________________ COMPATIBILITY OF POLYELECTROLYTE OF EXAMPLE I WITH COMMON SURFACTANTS - Surfactant % Surfactant Trade Name Chemical Name Type 1% 3% __________________________________________________________________________ Sulframin 40 Sodium alkyl aryl sulfonate anionic C C Sodium dodecylbenzene sulfonate do. C C Triton CF 10 Ethyloxylated alcohol nonionic C C Biosoft EA 10 Ethyloxylated fatty alcohol do. C C Hyamine 1622 Quat. ammonium cationic I I Hyamine 2389 Quat. ammonium cationic C C Versene 100 EDTA (ethylenediamine- tetraacetic acid) sequesterant C C Hamshire X100 NTA (nitrilotriacetic acid do. C C __________________________________________________________________________ Note: C = Compatible I = Incompatible

EXAMPLE XX

Corrosion Studies with Selected Metals

A series of static corrosion tests are conducted to determine the effects of the polyelectrolyte on metals. Specimens of copper, silver, stainless steel, aluminum, 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.

This study shows that the polyelectrolyte solution is less corrosive to steel and aluminum than the sodium tripolyphosphate solution. For silver and stainless steel, the corrosion is about the same for both solutions and of a low order. Copper is significantly corroded by both materials.

Table 4 __________________________________________________________________________ PARTIAL-IMMERSION CORROSION STUDY __________________________________________________________________________ Corrosion Test Solution Metals Weight Loss Corrosion Type Liquid-Vapor mg/sq ft (*) Liquid Phase Vapor Phase Interface __________________________________________________________________________ Polyelectrolyte of 1010 Steel 590 Rust None Not Visible Example I (10% Solution) 316 Stainless Steel 38 Not Visible Not Visible do. Copper 949 Tarnish Pits Black Pits Black Pits Silver 96 Not Visible Not Visible Not Visible Aluminum 78 Dull Dull Not Vis- ible Sodium Tripolyphosphate 1010 Steel 6,511 Rust and Pits Rust Heavy Rust (10% Solution) 316 Stainless Steel 0 None None None Copper 918 Lamulor Black Pits Black Pits Silver 76 Not Visible Not Visible Not Visible Aluminum 825 Bright Pits Dull Gray __________________________________________________________________________ Pits Note: (*) Submerged area only.

EXAMPLE XXI

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 detergents with and without polyelectrolyte. The exact product formula is shown in Table 5.

The soil cloth specimens are washed in the Tergetometer and the conditions are as follow:

Detergent Concentration 0.5% Wash & rinse Temperature 120.degree.F. Wash Time 10 min. Rinse Time 5 min. Cycles 1 wash - 3 rinses Water to Cloth Ratio 80:1 Dry Period 16 hr at 70.degree.F.

The specimens are evaluated using the "Gardner Multiplepurpose Reflectometer." Soil removal is calculated from the following formula:

(A - B)/(C - B) .times. 100 = % soil removal

where:

A = reflectance of soiled cloth after washing

B = reflectance of soiled cloth before washing

C = the reflectance of an unsoiled piece of the same cloth.

The soil redeposition on clean cloth is calculated as a redeposition index from the following formula:

D/C = redeposition index

where:

C = the reflectance of an unsoiled piece of the same cloth

D = the reflectance of the washed unsoiled cloth.

The closer the index is to one the less soil redepositioned and the better the detergent.

Table 5 presents the data and results of these experiments. The results of these experiments show that, when the isocyanurate-based polyelectrolyte is incorporated in the basic formula, it does clean significantly better, but has a slightly lower redeposition index. This difference in redeposition index is not significant. The nonphosphate counterpart of the basic formula, isocyanurate-based polyelectrolyte, cleans almost equally as well.

Table 5 __________________________________________________________________________ LAUNDRY DETERGENT COMPOSITION AND PERFORMANCE __________________________________________________________________________ Ingredients in Detergent Formulation Number Detergent Formulation 1.sup.a 2 3 4 5 6 __________________________________________________________________________ Ultra-sulfamin 40 30 g 30 g 40 g 40 g 40 g 40 g Sodium Tripoly Phosphate 50 g 45 g 0 0 0 0 Sodium Meta Silicate 18 g 18 g 20 g 20 g 20 g 20 g Sodium Carboxymethyl Cellulose 2 g 2 g 2 g 2 g 2 g 2 g Sodium Carbonate 0 0 23 g 18 g 23 g 20 g Sodium Citrate 0 0 10 g 15 g 10 g 0 Sodium Gluconate 0 0 0 0 0 13 g Polyelectrolyte.sup.b 0 5 g 5 g 5 g 10 g 10 g % Cleaning 3.29 4.06 2.99 2.87 3.50 2.80 Redeposition Index 0.976 0.970 0.967 0.964 0.974 0.974 __________________________________________________________________________ .sup.a This formulation is equivalent to "All" without borax and brighteners. .sup.b Polyelectrolyte of Example I.

EXAMPLE XXII

Automatic Dishwasher Detergent Formulation and Evaluation

When the polyelectrolyte of Example I is evaluated by formulating into a variety of automatic dishwasher detergent formulations and tested according to the Splash-Wash Tester Method described below, the results were as given in Table 6.

Table 6 __________________________________________________________________________ AUTOMATIC DISHWASHER DETERGENT EVALUATION* __________________________________________________________________________ Composition Formulation Number Performance 1 2 3 4 5 6 __________________________________________________________________________ Sodium tripoly- phosphate, g 55 55 -- -- -- -- Sodium silicate, g 25 20 50 50 50 50 Triton CF 10, g 3 3 3 3 3 3 Sodium carbonate, g 17 12 17 22 12 17 Sodium sesquicar- bonate, g -- -- 25 25 25 25 Polyelectrolyte of Example I, g -- 10 5 -- 10 5 Monsanto ACL 66 (chlorine bleach), g -- -- -- l-- -- 3 % Cleaning** 61.4 83.6 91.5 91.5 97.0 75.6 Redeposition*** 1.003 0.982 0.974 1.013 0.974 * Splash-Wash Tester Method, see below ** Average values obtained from three tests (each test containing four specimens). *** Average values obtained from three tests (each test contained two tes specimens).

SPLASH WASHER TEST METHOD

I. apparatus

A. Splash Washer

The splash washer is a plastic cylinder 5 in. in diameter, 81/2 in. long, sealed at the bottom with an outlet in the center for draining. An inlet is located on the side 11/2 in. from the bottom. An electric motor 1/70 hp, 1,500 rpm fits on the top and turns the agitator. The blades of the agitator are even with the inlet and are bent at a 45.degree. angle. A removable copper ring with six clips for holding test specimens rests on three screws 3 in. from the top.

B. Photometer

Hunter Photometric Unit with Reflectance Standards.

Ii. test Specimen Preparation

A. Pretreatment of Slides

Wash 18 microscope slides (3 in. .times. 1 in.) in soapy water, rinse and blot dry, free of spots. Twelve for soiling and six left clean.

B. 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: 1/2 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.

C. Application of Soil to Slides and Curing

Remove from refrigerator and mix until uniform.

Place mixture in spray-gun container and set air regulator at 50 psi spray pressure.

Hold spray-gun approximately 18 to 20 in. from slides and spray evenly a 2 in. .times. 1 in. area on one side of the slides. (Be extremely careful to avoid "runs.")

Allow sprayed slides to air-dry 15 min before placing in the oven at 120.degree.F. for 20 min.

Allow slides to come to room temperature before placing in splash washer.

D. Determination of Reflectance of Test Specimens with the Photometer

1. Allow unit to warm up for 45 min.

2. Zero the unit.

3. Set unit at a standard reflectance (depending upon whether a soiled or clean slide is to be measured) by using standards.

4. Place slide in holder, soiled side down. Read and record.

5. Read and record clean slides also.

Iii. testing Procedure

A. All Tests are Run in Triplicate

Four soiled and two clean test specimens for each run.

B. Placement of Test Specimens

Attach slides to clips on copper ring in the following manner. Soiled surface toward center in following sequence: two soiled, one clean, two soiled, one clean.

Place in splash washer.

C. Wash-Rinse Cycles

1. Add 300 ml of heated tap water (120.degree.F.) to 0.9 g of test material, mix well and add through inlet to washer.

2. Run for 10 min, then drain.

3. Add 300 ml clean heated tap water (120.degree.F.) to washer.

4. Run for 5 min then drain and repeat Step 3.

D. Remove Slides and Allow to Air Dry

Iv. determination of Results

1. Measure reflectance of washed test specimens as done in Part II, Section D.

2. calculation of results.

a. % Cleaning: is calculated for each soiled slide. The average of the 12 slides is the test result. 100% is optimum.

b. 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.

3. Formulas for calculation.

% Cleaning = (A-B)/(C-B) .times. 100%

Redeposition Index = D/C

a = reflectance washed soiled slide

B = Reflectance unwashed soiled slide

C = Reflectance unwashed unsoiled slide

D = Reflectance washed unsoiled slide

EXAMPLE XXIII

Water Softening Capability

When the polyelectrolyte of Example I is evaluated in water softening ability by formulation of a variety of solutions of water having relatively initial hardness and by measurement of the final hardness with the soap lather method, the results are as shown in Table 7. (See Betz Handbook of Water Conditioning 1947 Chapter 34, Hardness, Soap Lather Method.)

Table 7 __________________________________________________________________________ WATER SOFTENING* __________________________________________________________________________ Concen. Initial Hardness Final Hardness Hardness Compound (Wt. %) (ppm CaCO.sub.3) (ppm CaCO.sub.3)* Removed (%) __________________________________________________________________________ Sodium 0.1 520 254 51.2 Tripoly 0.05 520 480 7.7 Phosphate 0.025 520 510 1.9 Polyelectrolyte of Example I 0.1 520 220 57.7 0.5 520 260 50.0 0.025 520 265 49.0 75% Na.sub.2 CO.sub.3 0.1 589 505 14.3 25% Tartaric 0.5 589 545 7.5 Acid 0.025 589 580 1.5 75% Na.sub.2 CO.sub.3 0.1 589 468 20.5 25% Gluconic 0.5 589 565 4.1 Acid 0.025 589 585 0.7 75% Na.sub.2 CO.sub.3 0.1 527 190 63.9 25% Sodium 0.5 527 244 53.7 Citrate 0.025 527 375 28.8 __________________________________________________________________________ * Soap-lather method. **Average value of triplicate analyses.

Modifications of the Invention

It should be understood that the invention is capable of a variety of modifications and variations which will be made apparent to those skilled in the art by a reading of the specification and which are to be included within the spirit of the claims appended hereto.

Claims

What is claimed is:

1. An improved detergent composition consisting essentially of at least about 2 to about 70 weight percent of a surfactant and about 2 to about 20 weight percent of an isocyanurate-based polyelectrolyte, wherein said isocyanurate-based polyelectrolyte has the following chemical structure: ##SPC6##

wherein:

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

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, B, Al, 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, Ir, hydrogen and quaternary ammonium groups,

A = a monovalent organic radical,

R' = monovalent hydrocarbon or substituted hydrocarbon radical,

m = average number of trisubstituted isocyanurate rings and is a positive integer from 0 to about 400,

n = average number of isocyanuric acid and/or isocyanurate salt groups, and is a positive integer from 1 to about 10,000,

2m +n +1 = average number of divalent R groups and is a positive integer from 2 to about 110,000,

m + 2 = average number of A groups and is a positive integer from 2 to about 2,000,

and wherein there are no N-to-N bonds, no A-to-A bonds, and no R-to-R bonds.

2. A formulation according to claim 1 wherein 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.

3. Detergent compositions comprising isocyanurate-based 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 70 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: ##SPC7##

wherein:

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,

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, B, Al, 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, Ir, hydrogen and quaternary ammonium groups,

A = a monovalent organic radical,

R' = monovalent hydrocarbon or substituted hydrocarbon radical,

m = average number of trisubstituted isocyanurate rings and is a positive integer from 0 to about 400,

n = average number of isocyanuric acid and/or isocyanurate salt groups, and is a positive integer from 1 to about 10,000,

2m + n + 1 = average number of divalent R groups and is a positive integer from 2 to about 110,000,

m + 2 = average number of A groups and is a positive integer from 2 to about 2,000,

and wherein there are no N-to-N bonds, no A-to-A bonds, and no R-to-R bonds.

4. A 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.

5. A 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.

6. A process according to claim 3 wherein the sequestrate comprises from about 5 to about 15 percent based on the weight of the total formulation, and is selected from the group consisting of sodium citrate, sodium tartrate, or sodium gluconate.