US3763047A

US3763047A - Detergent compositions

Info

Publication number: US3763047A
Application number: US00139809A
Authority: US
Inventors: R Fairs
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1971-05-03
Filing date: 1971-05-03
Publication date: 1973-10-02
Anticipated expiration: 1990-10-02

Abstract

A granular detergent composition containing (a) a granular blend of mixed mono- and di-glycerides of fat-forming fatty acids, said mixture having a melting point of not less than 54*C. with a polyoxyethylene derivative of a higher fatty acid sorbitan ester; and (b) a compound selected from the group consisting of an inorganic water-soluble alkaline detergent salt, an inorganic alkaline sequestering agent, an organic alkaline sequestering agent and mixtures of these compounds. These compositions may contain an oxidizing agent of the oxygen releasing type or the halogen releasing type. These detergent formulations are useful for washing hard surfaces and are especially suitable for dishwashing machines and the like.

Description

Unite States Patent [1 1 Fairs Oct. 2, 1973 DETERGENT COMPOSITIONS [75] Inventor: Robert Roy Fairs, North Umberland, Pnmary "f" W wemblau England Att0rneyJulius P. Filcik, Charles R. Wilson and Richard C. Witte [73] Assignee: The Procter & Gamble Company,

Cincinnati, Ohio [57] ABSTRACT Filed! y 3, 1971 A granular detergent composition containing (a) a [211 App]- NOJ 139,809 granular blend of mixed monoand di-glycerides of fatforming fatty acids, said mixture having a melting point of not less than 54C. with a polyoxyethylene derivative of a fatty acid so bltan ester; and a com- 252/135, 252/351 ound selected from the group consisting of an inorlllltganic water soluble alkaline detergent alt an inorof Search 95, ganlc alkaline sequestering agent an organic alkaline 252/89, sequestering agent and mixtures of these compounds. These compositions may contain an oxidizing agent of References Cited the oxygen releasing type or the halogen releasing type. UNITED STATES PATENTS These detergent formulations are useful for washing 3,549,543 12/1970 Kirstachler 252/135 X hard surfaces and are especially suitable for 3,600,3l7 8/1971 Lintner.... 252/99 dishwashing machines and the 3,577,347 5/1971 Monickt. 252/99 2,830,906 4 1953 Farback 252 351 x 14 Claims, N0 Drawings 1 DETERGENT COMPOSITIONS BACKGROUND OF THE INVENTION The invention relates to granular detergent compositions intended primarily for washing hard surfaces, and especially suitable for use in dishwashing and the like machines. Such compositions are hereinafter called dishwashing compositions, and include compositions suitable for washing other hard surfaced articles, for example bottles, plastics articles, cutlery, metal goods, dairy equipment etc.

Known compositions of this type normally comprise a major proportion of alkaline substances such as alkaline inorganic salts,caustic alkalis, sequestering agents and oxidizing and sanitizing agents and the like, together with a minor, but important, proportion of one or more organic wetting agents.

Desirable properties of such dishwashing compositions include:

they should be free-flowing, even after prolonged storage, for easy handling and dispensing,

they should effectively remove soil, such as food residues, grease etc., from the surfaces and keep it in suspension during the washing process,

they should generate little or no foam in use, even in the presence of food residues, grease, etc.,

they should have bactericidal properties. In addition they should not corrode, tarnish or leave perceptible deposits upon the surfaces even after repeated washings.

If anionic detergents are used in these compositions in an amount sufficient to have appreciable wetting action, they cause excessive foam in use, the foam interfering with the scouring action of the detergent solution on the surfaces to be cleaned, and promoting carry over of soil-laden detergent solution from the washing cycle to the rinsing cycle of the machine. The lower foaming nonionic detergents are therefore more often employed, but most nonionic detergents are liquids or pastes at ordinary temperatures. Hence they tend to make granular compositions containing them sticky and non-freeflowing. Furthermore, for the same reason, they promote intimate contact between any chlorine-releasing oxidizing and sanitizing agents present in the composition, and encourage their decomposition during storage.

BRIEF DESCRIPTION OF THE INVENTION The present invention is based on the observation that these failings of known anionic and nonionic detergents and wetting agents can be avoided or reduced, and the desired characteristics of a dishwashing composition can be obtained, by using certain emulsifiers which have previously only been considered for use in food preparations, especially in frozen confections such as ice creams.

DETAILED DESCRIPTION OF THE INVENTION According to the invention there is provided a granu lar detergent composition comprising:

a. from 0.! percent to percent by weight of the composition of an organic surface-active agent which is a granular blend of 1) mixed monoand diglycerides of fat-forming fatty acids, said mixtures of glycerides having a melting point of not less than 54C., with (2) a polyoxyethylene derivative of a higher fatty acid sorbitan ester; and

b. from 80 percent to 99.9 percent by weight of the composition of a compound selected from the group consisting of l. inorganic water-soluble alkaline detergent salt, 2. an inorganic alkaline sequestering agent,

3. an organic alkaline sequestering agent and 4. mixtures of these compounds.

The above compositions are especially effective when in addition they contain an oxydizing agent. The oxydizing agent may be of the oxygen releasing type or of the halogen releasing type.

The organic surface active agents suitable for the compositions of the invention include those described in British patent specification No. 95 l ,0] l of Atlas Chemical Industries, Inc; and marketed under the Trade name Tween-mos."

Generally, the preferred organic surface active agents comprise a blend of from 95 to 60 percent by weight of mono and di-glycerides of fat-forming fatty acids, said mixture of glycerides having melting point not less than 54C, with from 5 to 40 percent of polyoxyethylene sorbitan tristearates containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan tristerate. Thus, a preferred organic surface active agent comprises a blend of 60 percent by weight of monoand di-glycerides of edible fats and oils, containing not less than 22 percent, by weight of the blend of monoglycerides, with 40 percent of a polyoxyethylated sorbitan tristearate containing an average of 20 moles of ethylene oxide per mole of sorbitan tristearate. The composition marketed as Tween-mos 280VS is particu larly preferred, and is said to have this constitution. Other suitable agents are Tween-mos 240VS said to comprise a blend of 80 percent monoand diglycerides of edible fats or oils containing not less than 30 percent by weight of the blend, of monoglycerides, with 20 percent of a polyoxyethylated sorbitan tristearate containing an average of 20 moles of ethylene oxide per mole of sorbitan tristearate; and a blend of from 97 to percent by weight of monoand diglycerides and from 3 to 30 percent by weight ofa polyoxyethylene sorbitan monooleate containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan monooleate; a preferred agent of this type is Tween-mos I00 VS, said to comprise a blend of percent monoand di-glycerides of edible fats or oils containing not less than 30 percent by weight of the blend, of monoglycerides, with 20 percent of a polyoxyethylated sorbitan monooleate containing an average of 20 moles of ethylene oxide per mole of sorbitan monooleate.

Normally, the stated organic surface active agent constitutes from about l percent to about 10 percent, especially about 2 to about 6 percent, by weight of the dishwashing compositions. Smaller quantities may be effective for some purposes, for instance down to 0.5 percent or as low as 0.1 percent. Larger quantities, up to 20 percent or more may be employed, especially in compositions intended for use at low concentrations. In general, the higher percentages of the organic surface active agent may provide insufficient improved performance to justify their cost.

It is most surprising that these compounds, previously known only as food emulsifiers, have now been found to be effective wetting and cleaning agents, and appear to be even more effective than the well known nonionic detergents, such as Pluronics (trade name), which are condensates of polypropylene oxide and polyethylene oxides; polyethoxyalkylphenols; polyethoxy alcohols and the like. They have the further advantages of being themselves granular solids at ordinary atmospheric temperatures (melting at 57C or higher), so that they do not cause stickiness in granular compositions in which they are incorporated. For the same reason, they do not promote intimate contact between oxygen or chlorine releasing agents and the other components of dishwashing compositions containing them. As a result of their limited solubility in water and their high melting point, they are particularly suitable for use in washing processes at relatively high temperature such as are commonly met in dishwashing and like machines, for instance at about 55C to boiling, preferably about 57C to 75C. They may also be used in manual dishwashing provided that temperatures over at least about 50C can be employed. In these conditions, the compositions of the invention generate little or no foam.

Apart from the small but essential proportion of organic surface active agent, the compositions of the invention comprise inorganic water soluble alkaline detergent salts, especially alkali metal, for example, sodium or potassium (especially sodium) carbonates and silicates; inorganic alkaline sequestering agents such as phosphates and polyphosphates, or borates; organic alkaline sequestering agents such as aminopolycarboxylates, for example, sodium nitrilo-triacetates or sodium ethylenediamine tetra acetates, and polyhydroxycarboxylates may be present. Other organic sequestering agents found to be useful in this invention include mellitates, benzene penta carboxylates, citrates, gluconates, oxydiacctates, oxydisuccinates and mixtures thereof.

The preferred inorganic components are penta sodium tripolyphosphate, tetra sodium pyrophosphate and sodium meta silicate.

Suitable oxidizing and sanitizing agents include peroxy salts such as sodium perborate, percarbonate, peroxy monosulphate and the like, and agents generating hypochlorite or hypobromite ions in solution such as chlorinated tri-sodium or other phosphates, and N- chloroor N-bromo-organic compounds such as sodium dichloroisocyanurate, trichloroisocyanuric acid, N-chloroand N-bromo-toluene or -benzene sulphonamide, and the like. These substances serve both to destroy bacteria and to oxidize certain components of the soil so that it is more readily removed in the washing process, and to minimize spotting of dishes etc., after drying, for example in heat, without wiping. Generally, preferred compositions contain a chlorine releasing agent, especially chlorinated trisodium phosphate or a chlorinated isocyanuric acid or a salt thereof.

The proportions of these compounds can be varied within wide limits according to the required properties of the composition. Thus very effective compositions contain from about 10 to 80 percent, especially 20 to 50 percent, sodium tripolyphosphate, anhydrous, preferably in granular form (for example such that not more than 20 percent passes a 100 mesh BSS sieve); from 5-60 percent sodium silicate, preferably anhydrous sodium meta silicate, but any solid, optionally hydrated, sodium silicate having weight ratio SiO,:NA O in the range [:1 to 3.4:1 may be used; from to about 30 percent of anhydrous sodium carbonate, preferably in dense granular form; a source of hypochlorite ion, in amount providing from about 1 to percent of available chlorine, such as sodium dichloroisocyanurate, trichlorocyanuric acid, or chlorinated trisodium phosphate. From 0 to percent of an oxidizing agent such as the alkali perborates, percarbonates and perox- 5 ymonosulphates may be used. Generally the amount of sodium silicate, especially sodium meta silicate, should not exceed about 70 percent and that of sodium carbonate should not exceed about 30 percent, since higher levels may cause some attack on glass or glazed surfaces. This composition should preferably contain insufficient moisture completely to hydrate the hydratable salts present. The remainder comprising from O to 30 percent anhydrous sodium sulfate.

The term available chlorine as used above and hereinafter presents the level of molecular chlorine (C1 having equal bleaching power. Since one atom of active chlorine in compounds providing hypochlorite ions in solution has the same activity as one molecule (i.e., two atoms) of molecular chlorine, the percentage of available chlorine stated, by weight, is double the weight percentage of reactive chlorine. Thus for example pure sodium hypochlorite, having the formula NaOCl would contain 47.7 percent reactive chlorine by weight, expressed as 95.4 percent available chlorine.

Neutral fillers, such as sodium chloride, sodium sulphate etc. may be present, for instance, from 0 to about 30 percent of sodium sulphate (calculated as anhydrous salt). Various other components may be included for various purposes, such as perfume, colouring matters, tarnish inhibitors such as benzotriazole, iron chelating agents, such as sodium gluconate, which prevent development of stains on aluminum and a haze-like deposit on glazed surfaces after repeated washing. Though not usually necessary or desirable other organic wetting agents and other sanitizing agents may be included in special cases.

The above mentioned inorganic salts may be at least partially hydrated when incorporated in the composition, provided that the free flowing properties of the composition are not impaired. Thus there should normally be sufficient hydrate-forming capacity available to absorb any moisture added during preparation of a product, (as explained below) and to enable the product to remain free flowing despite normal changes of humidity of the atmosphere to which it is exposed.

The compositions may be prepared by any effective method. Conveniently the dry particulate components, for example, salts, Tween-mos compounds, but excluding the oxidizing or chlorine-releasing agent, may be mixed together in any suitable apparatus, such as a rotating drum or cube mixer, inclined pan mixer etc. Liquid components such as perfume and/or an aqueous dispersion of colouring matter are admixed, most conveniently by spraying them on the particular mixture. Any water present or added is absorbed by incompletely hydrated salts in the composition. Finally the oxidizing or chlorine-releasing agent is added as a particulate solid.

The following Examples illustrate the invention:

EXAMPLE I The following compositions were prepared by dry mixing the first four components listed, spraying on thoseso indicated, and finally dry mixing the chlorinated trisodium phosphate.

A percent Composition by by weight weight Anhydrous granular sodium tripolyphosphate 45.2 45.5 Anhydrous sodium metasilicate (beads) 11.00 11.00 Sodium Silicate "M (Crystalline hydrate,

SiO,: Na,O:3.3:l by weight). 11.00 11.00 Tween-mos 280VS 2 Pluronic L62 2 Perfume sprayed on 0.1 0.1 Dyestuff do. 0002 0.002 Water do. 07 0.4 Chlorinated trisodium phosphate (containing about 3% available chlorine by weight) 30 30 Composition A was according to the invention and was a free flowing dry powder. The reference composition B was a slightly sticky powder, tending to form soft lumps on standing. Their cleaning efficiency was determined by using them in a Kenwood Model A 1212 Dishwashing machine, using its operating cycle 11, at a concentration of 0.75 percent by weight in water 12H (172 ppm hardness as CaCO In the machine, water temperature was 57-60C. To provide a representative load for the machine 44 dinner plates, used in a Canteen for a main luncheon course, i.e., meat, fish etc., were obtained and half were washed with each detergent composition. After washing in the machine the number of soil marks remaining was counted. The plates were then carefully hand washed, and dried, for re-use. This was repeated for a total of five washes. In every wash the number of marks on plates washed by the composition A of the invention was less than that on plates washed by the reference composition B, and overall the average values were: Product of the invention 1.1 marks per plate, Reference product 1.8 marks per plate.

EXAMPLE 11 Similar washing performance was provided by the following compositions, which also were dry free flowing powders. They contained additives which reduced the tendancy of the inorganic components to tarnish cutlery and they reduced the staining of aluminum in the presence of iron-bearing water or soil. The quantities are percentages by weight.

Products C and D are intended for use at about 1% concentration in the wash liquor; product E, for use at about 0.5% concentration.

EXAM PLE 111 Compositions of the following formula were prepared and their cleaning performance tested as in Example l, except that tests were replicated two or three times as indicated below:

X: by weight 40.4

Sodium tripolyphosphate Sodium metasilicate 13.5 Sodium silicate (SiO,:Na,O by

weight 3.311) 13.5 Chlorinated trisodiumphosphate 30.1

Color/water/perfume Organic detergent Our EXAMPLE 1 Granular compositions of the formula given in Example 111, containing Tween-mos 280 VS as organic detergent, and for comparison Pluronic L 62 (Trade name) were prepared. The products were packed in cardboard sided lever-lid canisters and stored in (1) a constant temperature room maintained at 26.5C., and (2) in a warehouse whose temperature varied without special control from about 265C. to about 0C. The percentage losses by weight of available chlorine after the stated times were:

265C. Warehouse Room Tween-mos product 4 months 31% 6 months 46% 7 Pluronic product 4 months 63% 6 months 78% 34 Having fully described the invention, what is claimed l. A granular detergent composition comprising:

a. from 0.1% to 20% by weight of the composition of an organic surface-active agent which is a granular blend of (1) mixed monoand diglycerides of fatforming fatty acid, said mixtures of glycerides having a melting point of not less than 54C., with (2) a polyoxyethylene derivative of a higher fatty acid sorbitan ester which contains an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan ester; and

b. from 80 percent to 99.9 percent by weight of the composition of a compound selected from the group consisting of 1) inorganic water-soluble alkaline detergent salt, (2) an inorganic alkaline se questering agent, (3) an organic alkaline sequestering agent and (4) mixtures of these compounds.

2. The composition of claim 1, wherein component (a) is a blend of from to 60 percent by weight of said glycerides and from 5 to 40 percent by weight ofa polyoxyethylene sorbitan tristearate containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan tristearate.

3. The composition of claim 1, wherein component (a) is a blend of from 97 to 70 percent by weight of said glycerides and from 3 to 30 percent by weight ofa polyoxyethylene sorbitan monooleate containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan monooleate.

4. The composition of claim 2, wherein component (a) is a blend of 60 percent by weight of monoand diglycerides of edible fats and oils, containing not less than 22 percent by weight of the blend, of monoglycerides, with 40 percent of a poly-oxyethylated sorbitan tristearate containing an average of 20 moles of ethylene oxide per mole of sorbitan tristearate.

5. The composition of claim 2, wherein component (a) is a blend of 80 percent by weight of monoand diglycerides of edible fats and oils, containing not less than 30 percent by weight of the blend of monoglycerides, with 20 percent of polyoxyethylated sorbitan tristearate containing an average of 20 moles ethylene oxide per mole of sorbitan tristearate.

6. The composition of claim 3, wherein component (a) is a blend of 80 percent by weight of mono and diglycerides of edible fats and oils, containing not less than 30 percent by weight of the blend, of monoglycerides, with 20 percent of a polyoxyethylated sorbitan monooleate containing an average of 20 moles of ethylene oxide per mole of sorbitan monooleate.

7. The composition of claim 1 which also includes an amount of chlorine releasing agent sufficient to provide from 1 percent to 5 percent available chlorine.

8. The composition of claim 7 wherein the chlorinereleasing agent is a chlorinated isocyanuric acid or salt thereof.

9. A composition as claimed in claim 7 wherein the chlorine-releasing agent is chlorinated trisodium phosphate.

10. The composition of claim I which also includes from 0 percent to 20 percent by weight of the composition an oxidizing agent selected from the group consisting of perborates, percarbonates and peroxy monosulphates.

11. The composition of claim 1 wherein component (b) (3) is selected from the group consisting of water soluble citrates, mellitates, benzene penta carboxylates, oxydiacetates, oxydisuccinates, gluconates, and mixtures thereof.

12. The composition of claim 1 wherein component (b) is from 10 to percent of anhydrous sodium tripolyphosphate, from 5 to 60 percent of sodium silicate having a weight ratio SiO to Na O in the range of from 1:1 to 3.4:1, a source of hypochlorite ion in an amount providing from 1 to 5 percent of available chlorine, from 0 to 30 percent of anhydrous sodium carbonate and from 0 to 30 percent anhydrous sodium sulfate.

13. The composition of claim 1 wherein there is present from 1 percent to 10 percent by weight of component (a).

14. The composition of claim 1 wherein there is present from 2 percent to 6 percent of component (a).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,763,047 October 2, 1973 Patent No. Dated Inventor) Robert Roy Fairs It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Columfi ine :54 "compounds" should ead "components-- Column 4, linehlS "presents should read -rep resents Column 5, line53 (isooyanurate should read -isocyanurate Column 6, line 32 "78% under Warehouse column" should read -78% under. Room" column 1 Column 7, line l8, fdhlorine" should read -a chlorine-- Signed and sealed this 27th day of August 1974 (SEAL) Attest:

' MCCOY M. GIBSONQCQIR. a c. MARSHALL DANN Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 ,763,047 7 Dated October 2, 1973.

Patent No.

Inventor) Robert Roy Fairs It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3 line "54 "compounds" should read -'-components- Column 4 line" 15 "presents" should read -rep resents-- Column 5 line 53 (isocyanurate should read --isocyanurate-- Column 6 line" 32 "78% under Warehousecolumn"- should read --78% under Room' columrv- Column 7 line l8 "chlorine" should read -a tzhlorine-Q Signed and sealed this 27th day of August 1974 (SEAL) Attest:

McCOY M. srBsoNfJR. n r c. MARSHALL DANN Attesting Offier r I Commissioner of Patents

Claims

2. The composition of claim 1, wherein component (a) is a blend of from 95 to 60 percent by weight of said glycerides and from 5 to 40 percent by weight of a polyoxyethylene sorbitan tristearate containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan tristearate.
3. The composition of claim 1, wherein component (a) is a blend of from 97 to 70 percent by weight of said glycerides and from 3 to 30 percent by weight of a polyoxyethylene sorbitan monooleate containing an average of from 8 to 50 moles of ethylene oxide per mole of sorbitan monooleate.
4. The composition of claim 2, wherein component (a) is a blend of 60 percent by weight of mono- and di-glycerides of edible fats and oils, containing not less than 22 percent by weight of the blend, of mono-glycerides, with 40 percent of a poly-oxyethylated sorbitan tristearate containing an average of 20 moles of ethylene oxide per mole of sorbitan tristearate.
5. The composition of claim 2, wherein component (a) is a blend of 80 percent by weight of mono- and di-glycerides of edible fats and oils, containing not less than 30 percent by weight of the blend of mono-glycerides, with 20 percent of polyoxyethylated sorbitan tristearate containing an average of 20 moles ethylene oxide per mole of sorbitan tristearate.
6. The composition of claim 3, wherein component (a) is a blend of 80 percent by weight of mono- and di-glycerides of edible fats and oils, containing not less than 30 percent by weight of the blend, of mono-glycerides, with 20 percent of a polyoxyethylated sorbitan monooleate containing an average of 20 moles of ethylene oxide per mole of sorbitan monooleate.
7. The composition of claim 1 which also includes an amount of chlorine releasing agent sufficient to provide from 1 percent to 5 percent available chlorine.
8. The composition of claim 7 wherein the chlorine-releasing agent is a chlorinated isocyanuric acid or salt thereof.
9. A composition as claimed in claim 7 wherein the chlorine-releasing agent is chlorinated trisodium phosphate.
10. The composition of claim 1 which also includes from 0 percent to 20 percent by weight of the composition an oxidizing agent selected from the group consisting of perborates, percarbonates and peroxy monosulphates.
11. The composition of claim 1 wherein component (b) (3) is selected from the group consisting of water soluble citrates, mellitates, benzene penta carboxylates, oxydiacetates, oxydisuccinates, gluconates, and mixtures thereof.
12. The composition of claim 1 wherein component (b) is from 10 to 80 percent of anhydrous sodium tripolyphosphate, from 5 to 60 percent of sodium silicate having a weight Ratio SiO2 to Na2O in the range of from 1:1 to 3.4:1, a source of hypochlorite ion in an amount providing from 1 to 5 percent of available chlorine, from 0 to 30 percent of anhydrous sodium carbonate and from 0 to 30 percent anhydrous sodium sulfate.
13. The composition of claim 1 wherein there is present from 1 percent to 10 percent by weight of component (a).
14. The composition of claim 1 wherein there is present from 2 percent to 6 percent of component (a).