US3303136A - Detergent compositions - Google Patents

Description

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bi 't. 3% Kiri-Litur- ZOE UH 3,303,136 Patented Feb. 7, 1967 3 303 136 ing a soiled tile into quarters. One of the soiled quarters i was washed in a standard manner with solution (1). DETERGENT COMPOSITIONS The second quarter was washed with solution (2). The

Willard M. Bright, Ridgewood, NJ., assignor to Lever third quarter was washed with solution (3). The fourth 33%; Company New York corpomhon of 6 quarter was kept as an unwashed control. tile was No Drawing Filed Feb 26, 1963, Ser. No 261,193 used for each series of three solutions evaluat ng a given 6 (313mm (CL 252.133) sulfonate. The washed tiles were inspected visually and ranked for cleanliness by a panel of three observers. The The present invention relates to detergent composifollowing hydrotropes were evaluated: sodium orthotions and to improvements in the cleaning of hard sur- 10 xylenesulfonate, sodium metaxylenesulfonate, potassium faces. More particularly, it pertains to polyphosphateparaxylenesulfonate, sodium toluenesulfonate, sodium aryl sulfonate compositions having synergistic cleansing ethylbenzenesulfonate, and sodium isopropylbenzenesulproperties. fonate.

Materials which aid in producing homogeneous liquids Details of the test from substances which are incompatible in aqueous media are known as y p Short chain alkyl y 5111- The details of soiling, washing and ranking follow: fonates have been used to solubilize the longer chain s0iIing -The floor m used were 9 inches x 9 inches alkyl y 0f sulfonates and other Organic detergents in Armstrong Asphalt Tile, factory finished, Pattern D-900 the Presence of complex, inorganic p p Ivory Marble, /s inch gage. A layer of vacuum cleaner ever, it has 11m bun generally IecOgniZcd that these dust (screened through 80 mesh to remove larger conventional hydrotropes also possess detergent properties since compositions containing polyphosphates and short chain alkyl aryl sulfonates have always contained synthetic detergents to provide suitable detergent activity to the formulations. Specifically, it has not been recognized that products containing a polyphosphate and these hydrotropic agents are particularly efiicacious in cleaning hard surfaces such as tiles and other coverings for floors, walls and the like.

It is an object of this invention to provide detergent compositions having synergistic cleansing characteristics.

Another object is to take advantage of the discovery that short chain alkyl aryl sulfonates contribute significantly to the detersive properties of formulations containing complex inorganic polyphosphates.

Still another object of the invention is to provide a means for efficiently cleansing hard surfaces.

It has now been found that certain sulfonates conventionally used as hydrotropes have enhanced tolerance for condensed phosphates and that such polyphosphatesulfonate compositions exhibit synergistic properties in cleaning hard surfaces such as painted walls, floor tile and the like.

The polyphosphate-sulfonate mixtures according to this particles) was rubbed evenly over the surface with a cloth. Any excess loose dust was shaken from the tile, and the area now soiled with adhering dust was covered with three successive layers of liquid floor wax (this operation simulated waxing a normally solid floor). Each layer of wax was allowed to dry in air before the next layer was applied.

Washing.The method of washing consisted of dipping a 3 inches x 4 inches swatch of new clean white terry cloth into the detergent solution, squeezing excess liquid from the fabric and rubbing each soiled area in a standard manner for 30 seconds. The loosened soil-detergent mixture was then wiped from the surface with a new clean 5 inches x 9 inches Wipette (an absorbent cellulose napkin).

Grading and ranking.The quarters of each tile were compared for cleanliness by a panel of three observers under standard daylight lighting conditions. The cleanest quarter was ranked 1, the next cleanest 2, the next cleanest 3 and the least clean 4.

The results of tests performed on the solutions described above are tabulated below. The symbol TKPP designates tetrapotassium pyrophosphate.

invention contain from about 40% to about 85% of at least one water-soluble salt of a polyphosphate and from Cleanness g Quarter ashed about 15% to about 60% of at least one water-soluble arylsulfonate. The proportions are based on dry mixultanate Series tures of these twoingredients. The polyphosphates used s gig: g gg in these compositions include tetrapotassium and tetrao e ggg sodium pyrophosphate, sodium and potassium tripolyphosphates and mixtures of these ingredients. The 5141; EAR which can be used include the alkali metal and 3 2 1 4 ammonium salts of benzene sulfonate, ortho-, meta-, and Sodium meta-xylenewb ionate 3 2 1 4 para-xylene sulfonate and mixtures of these isomers, pgmssium pmqylenesul- 2 2V 1 4 onate.

toluene sulfonate, ethylbenzene sulfonate, n propyl and sodium toluenesulmnatem 3 2 2 z 1 4 isopropylbenzene sulfonate, etc. as well as various comsodium ethylbenzenesul binations of these materials. ggg ig 1 4 It is within the scope of the present disclosure that 110mm 3 2 1 4 such additional ingredients as fillers, colorants, perfumes,

optical dyes, bleaches, and germicides may be added.

The following examples serve to illustrate'the present invention, without however, limiting the same thereto.

EXAMPLE 1 NOTE l.A ranking of is given to indicate the median when two detergents are tied for two adjacent ranks. Thus, a ranking of "28/ indicates that a tie occurred for 2 and 3 ranks and, l indicates gist a Se occurred for 1" and 2 ranks, i.e., "cleanest" and "next to eanes It was necessary to warm the sodium ortho-xylene-sulfonate solution, and the solution of the sodium orthoxylenesulfonate-TKPP mixture to melt crystals before use.

It was necessary also to warm the potassium paraxylenesulfonate solution to melt the crystals. However, these crystals reformed as soon as the warmed solution was touched to the cold tile. Crystals were not removed from the mixture of potassium para-xylenesulfonate and TKPP even with warming, and when used this solution contained a small amount of crystals.

EXAMPLE 2 The following results were obtained using mixtures of tetrapotassium pyrophosphate (TKPP) and commercial sodium xylenesulfonate (SXS) for cleaning a standard soiled wall surface. Five solutions of tetrapotassium pyrophosphate of varying concentrations were each used in combination with various concentrations of the sulfonate. Various percentage concentrations of tetrapotassium pyrophosphate in water solutions, namely: 22.5%, 21.0%, 18.0% and were each tested with 8.0%, 6.9%, 4.6% and 0% of sodium xylenesulfonate. For these tests, 0% of either tetrapotassium pyrophosphate or sulfonate was considered a concentration level of that component.

A panel of white Walltex, 4 feet x 2 feet, was attached with tape to a wooden table top. The surface was evenly soiled by application of a mixture of screened vacuum cleaner dust, oildag (colloidal graphite and petroleum oil) and cooking fat (bacon grease). An ordinary 9 inch paint roller was used in applying the soil evenly. The application of soil was adjusted to bring the soiled reflectance to a level of 17% on the Hunter reflectometer equipped with a green filter. The Hunter reflectometer is standardized so that the reflectance of a magnesium oxide block is 100% (green filter). For each run this test panel was divided into fifths, lengthwise, making five equal-sized rectangular test areas.

Washing of soiled areas.The washing of the soiled area was conducted at levels of 22.5%. 21.0%, 18.0% and 0% TKPP in combination with 8.0%, 6.9%, 4.6% and 0% of SXS. Solutions of each component identified by numerals for tetrapotassium pyrophosphate and letters for sodium xylenesulfonate were prepared so that equal weight portions of each component would give the desired mixtures.

Percent- Cone. of Prepared Solutions To illustrate-la called for equal weights of 1) 45% TKPP and (a) 16% SXS giving a resultant mixture (1a) of 22.5% TKPP and 8.0% SXS.

The washing scheme was as follows:

The above prepared solutions were used at room temperature in a standardized manner, 20 milliliters of solution placed in a inch watch glass. A clean white piece (3 inches x 4 inches) of new terrycloth was dipped into the solution until the cloth became saturated. The fabric was removed, squeezed between the fingers to remove excess moisture, and rubbed over the rectangular soiled Walltex test area for 30 seconds. The dirt and detergent mixture left on the test area was removed by absorption with an absorbent tissue. After drying, the reflectance of the tested area was determined in four locations.

When the test washings had been completed, the test area of 9.6 inches x 2 feet was cut from the larger 2 feet x 4 feet panel of Walltex used for each run. The resultant smaller swatch was easier to handle during the reflectance determinations on the Gardner color difference meter. Each cleaned area was read four times along the longer central axis. Since there were four replicates for each 4 detergent, the reflectances shown in Table H are the averages of 16 readings for each detergent mixture.

TABLE 11 [Average reflectance of standard soiled Walltex panels after washing] Percent Sodium Xylenesulfonate Percent TKPP 22. 64. 9 64. T 64. 0 52. 5 21. 64. 3 G3. 6 05. 5 55, 4 18. 61. 9 6i. 5 62. 0 4R. 9 0. 41. 4 42. 9 40. 7 37. 5

EXAMPLE 3 Additional tests were conducted using the same procedure as described in Example 2 employing a 24% concentration of TKPP and a 13.8% concentration of SXS so that combining equal weights of the TKPP solution with the SXS solution gave a mixture containing 12% TKPP and 6.9% SXS. The following reflectances were observed.

TABLE III [Average reflectance of standard soiled Walltex panels after washing] Conc. Sodium Xylenesulionnte Cone. TKPP, Percent EXAMPLE 4 Additional tests were conducted with a combination of 70% tetrapotassium pyrophosphate and 30% tetrasodium pyrophosphate (TSPP) with ortho-, meta-, and paraxylene-sulfonates, and 50-50 mixtures of these isomers.

The following mixtures were tested:

TABLE IV [All percentages are by weight] Percent Percent Percent Solution Percent Percent Ortho- Meta' Parn- Number TKPP TSPP SXS SXS SS5 Samples 1, 4, 6, 7, 8 and 9 contained crystals. These mixtures were heated to 50 C. (122 F.) to dissolve the separated solid material and were used at this temperature; the remaining solutions were used at room temperature F.).

Each soiled panel was divided into 5 test areas, as described in Example 2. The test solutions were used in a random fashion until four replicate washings had been made with each mixture. The standardized washing Percent Sodium Xylene Sultonate Comm. Grade.

method was used and the reflectances ot the cleaned areas were determined as follows:

TABLE V [Average reflectance of washed standard soiled panels] Percent Percent Percent Percent Percent Unadjusted Solution TKPP TSPP Ortho- Meta- Para- Reflectance SXS SXS SXS than those values obtained by adding the adjusted reflectance for the sulfonate alone and those for the pyro- Adjusted Reflectance Nora-The reflectances were adjusted for the water blank by cl a panel washed in water alone; thus, the adjusted figure shows solution, over and above that done by water.

These results indicate that solutions containing the tetra-phosphate mixture plus sulfonate (either a single isomer or mixed isomers) are superior to the combined results of solutions containing phosphate alone, or sulfonate alone.

EXAMPLE 5 Additional tests were conducted to determine the reflectances obtained from mixtures of pyrophosphates alone, sulfonates alone, and sulfonate mixtures alone. The results are tabulated below:

TABLE VI [Average reflectance of washed test areas] subtracting the reflectance the cleaning done by the phosphate alone. This clearly demonstrates the synergism of the present invention.

EXAMPLE 6 Further tests were performed on a series of mixtures to determine their eflFectiveness in cleaning hard surfaces. The products were evaluated as described in Example 2 by washing a Walltex board soiled in a standard manner. The reflectance of each swatch of the wall covering was measured on the Gardner color dififerencc meter.

The mixtures received as solutions were used in the Percent Percent Percent Percent Percent Unadjusted Solution TKPP TSPP Ortho- Meta- Para- Reflectance SX S 5X S SX S Adjusted Reflectance tests as is without dilution. All solutions were heated to about 110 F. before use. Powdered Product 6 was utilized by dissolving 32.5 grams of the mixture in 67.5 ml. of distilled water. A washing temperature of 110 F. was maintained in all tests.

TABLE VII [Composition oi products and reflectance of washed Walltex with adjustment for reflectance oi water blank] Product Number Soln.

Percent Penta Sodium Tripolyphosphate Percent Penta Potassium Tripolyphosphate Percent Calgon"-Mainly Hexametaphosphate (NaPOa)a- Percent Ammonium Xylene Sulior Percent Tetra Potassium Pyrophosphate.

Percent Sodium Silicate Solids (SiO,:Nai0=2.0) Percent Perfumes Percent Blue Dye (Hastings S liy Blue") Percent Sodium Benzene Sullonate.

Percent Fluorescent Dye e Percent Potassium Dichloroisocyanurate.

Percent Sodium Metasilicate, Solids.

Percent Germicide 2. 77 Percent Water 69. 5 09. 5 69. 5 74. 0 36. 5 7. 60 69. 5 100. 0 69. 5 Percent Total 100.00 100. 0 100.00 100. 0 100 100. 00 100. 0 100. 0 100. 0 Average Reflectance of Washed Sw Color Difference Meter 26. 9 30. 2 48. 7 31.1 57. 0 48. 7 54. 5 18.1 51. 1 Average Reflectance Minus Water Blank, or ControL. 8. 8 12. l 30. 6 13. 0 38. 9 30. 6 36. 4 0. 0

I 4-4'bis "-morphilino-fi" anilino-l",3, "-triazin-2-ylamino)-stilbene-2,2-disuiionic acid, Na salt.

b Approx. equal parts by weight oi 4,5-dibromoand 3,4',5-tribromosa1lcylanilide.

It is seen from the above data that Product 4 containing hexametaphosphate is not within the scope of the invention since no synergistic results are obtained. However, the pH of this product was about 5 while the pH of other formulations within the scope of the invention was higher than 7, i.e., on the alkaline side. It will be recognized that the lack of synergism in Product 4 may be due to the relatively low pH and that this can be overcome by means well-known to those skilled in the art.

Moreover, it is evident from Product 6 above that compositions containing the polyphosphate and sulfonate of the invention can be marketed as dry powders and the ultimate consumer may add water before using if desired.

Additives which do not materially alter the beneficial characteristics of the mixtures of this invention may be incorporated as shown in the above table. The amount of the additives should not exceed about 45% based on the weight of the dry ingredients. Thus, up to about 3% of a germicide and 3% of sodium silicate solids can be presem, as well as a maximum of about 10% of a chlorinereleasing bleaching agent. Other inert ingredients up to the 45% maximum can be added.

The term Walltex as used in the above examples refers to a coated cotton fabric waterproof wall covering which may be applied with paste in much the same manner as wall paper.

It will occur to those skilled in the art that there are many modifications to this invention as specifically described therein. It is intended to include all such modifications within the scope of the appended claims.

What is claimed is:

1. A composition consisting essentially of about 40% to about 85% of a water-soluble condensed, inorganic polyphosphate and from about to about 60% of a water-soluble aryl sulfonate selected from the group consisting of benzenesulfonate, ortho-xylenesulfonate, metaxylenesulfonate, para-xylenesulfonate, toluenesulfonate, ethylbenzenesulfonate, n-propylbenzenesulfonate, isopropylbcnzenesulfonate and mixtures thereof, the proportions being based on the weight of the dry ingredients, said composition providing an alkaline reaction in aqueous solution.

2. A composition consisting essentially of about 40% to about 85% of a water-soluble condensed, inorganic polyphosphate, about 15% to about 60% of a watersoluble aryl sulfonate selected from the group consisting of benzenesulfonate, ortho-xylenesulfonate, meta-xylenesulfonate, para-xylene sulfonate, toluenesulfonate, ethylbenzenesulfonate, npropylbenzenesulfonate, isopropylbenzenesulfonate and mixtures thereof, up to about 10% of a chlorine-releasing agent, up to about 3% of a germicide and up to about 3% of a sodium silicate, the proportions being based on the weight of the dry ingredients, said composition providing an alkaline reaction in aqueous solution.

3. An aqueous dispersion of the composition recited in claim 1.

4. An aqueous dispersion of the composition recited inclaim 2.

5. A method which comprises cleansing a hard surface by contacting therewith a composition consisting essentially of about 40% to about 85% of a condensed inorganic water-soluble polyphosphate and from about 15% to about of a water-soluble aryl sulfonate selected from the group consisting of benzenesulfonate, ortho-xylenesulfonate, meta-xylenesulfonate, para-xylenesulfonate, toluenesulfonate, ethylbenzenesulfonate, n-propylbenzenesulfonate, isopropylbenzenesulfonate and mixtures thereof, the proportions being based on the weight of the dry ingredients, said composition providing an alkaline reaction in aqueous solution.

6. A method which comprises cleansing a hard surface by contacting therewith a composition consisting essentially of about 40% to about of a condensed, inorganic water-soluble polyphosphate, from about 15% to about 60% of a water-soluble aryl sulfonate selected from the group consisting of benzenesulfonate, ortho-xylenesulfonate, meta-xylenesulfonate, para-xylenesulfonate, toluenesulfonate, ethylbenzenesulfonate, n-propylbenzenesulfonate, isopropylbenzenesulfonate and mixtures thereof, up to about 10% of a chlorine-releasing agent, up to about 3% of a ger-micide and up to about 3% of a sodium silicate, the proportions being based on the weight of the dry ingredients, said composition providing an alkaline reaction in aqueous solution.

References Cited by the Examiner UNITED STATES PATENTS 2,634,240 4/1953 Showalter ct al. 252138 XR 3,030,312 4/1962 Mills 252161 3,035,054 5/1962 Symes et al 25299 XR 3,037,935 6/1962 Tidridge et al 252138 X 3,064,048 11/1962 Schramrn et al. 252106 XR 3,066,104 11/1962 Dasch et al 252138 XR 3,134,711 5/l964 Reller et al 252106 XR LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, Examiner.

J. T. FEDIGAN, Assistant Examiner.

Claims (1)

1. A COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 40% TO ABOUT 85% OF A WATER-SOLUBLE CONDENSED, INORGANIC POLYPHOSPHATE AND FROM ABOUT 15% TO ABOUT 60% OF A WATER-SOLUBLE ARYL SULFONATE SELECTED FROM THE GROUP CONSISTING OF BENZENESULFONATE, ORTHO-XYLENESULFONATE, METAXYLENESULFONATE, PAPA-XYLENESULFONATE, TOLUENESULFONATE, ETHYLBENZENESULFONATE, N-PROPYLBENZENESULFONATE, ISOPROPYLBENZENESULFONATE AND MIXTURES THEREOF, THE PROPORTIONS BEING BASED ON THE WEIGHT OF THE DRY INGREDIENTS, SAID COMPOSITION PROVIDING AN ALKALINE REACTION IN AQUEOUS SOLUTION.