WO1997007188A1

WO1997007188A1 - Hand dishwashing powder with chlorine bleach

Info

Publication number: WO1997007188A1
Application number: PCT/US1996/012190
Authority: WO
Inventors: Carolina Buitron Kellstein; Artemio Castro
Original assignee: The Procter & Gamble Company
Priority date: 1995-08-18
Filing date: 1996-07-29
Publication date: 1997-02-27
Also published as: MX9801320A

Abstract

The subject invention involves dry particulate detergent and bleach compositions comprising: (a) at least about 18 % anionic surfactant; (b) from about 1 % to about 20 % silicate builder; and (c) a chlorine bleach material which provides from about 0.003 % to about 4 % available chlorine. The subject invention also involves methods of cleaning cooking or eating utensils by hand washing them in aqueous dispersions of such compositions.

Description

HAND DISHWASHING POWDER WITH CHLORINE BLEACH

TECHNICAL FIELD

The subject invention involves detergent and bleach compositions intended for use in hand washing of eating and cooking utensils.

BACKGROUND OF THE INVENTION

In many parts of the world, improved products for cleaning and sanitizing eating and cooking utensils is needed.

It is an object of the subject invention to provide dry particulate detergent and bleach compositions for hand washing and sanitizing of eating and cooking utensils.

It is also an object of the subject invention to provide methods of cleaning and/or sanitizing eating and cooking utensils by hand washing them with such compositions.

SUMMARY OF THE INVENTION

The subject invention relates to dry particulate detergent and bleach compositions comprising:

(a) at least about 18% anionic surfactant;

(b) from about 1 % to about 20% silicate builder; and

(c) a chlorine bleach material which provides from about 0.003% to about 4% available chlorine.

DETAILED DESCRIPTION OF THE INVENTION The subject invention involves dry particulate detergent and bleach compositions. The "dry particulate" compositions are not necessarily moisture- free, but are flowable powder or granular products which are essentially dry to the touch.

Materials incorporated in the detergent and bleach compositions of the subject invention include those indicated hereinbelow. Unless otherwise specified, all percentages are on a weight basis.

As used herein, "alkyl" means hydrocarbyl moieties which are straight or branched, saturated or unsaturated with one or more double bonds. As used herein, "alkanyl" means saturated alkyl and "alkenyl" means alkyl unsaturated with double bonds. Alkyl may be of single or mixed lengths, and are often mixed lengths and saturation derived from natural sources such as tallow, coconut oil, palm oil, etc. Anionic Surfactants

The subject invention compositions comprise at least about 18% anionic surfactant, preferably from about 20% to about 40%, more preferably from about 22% to about 36%, more preferably still from about 24% to about 32%, still more preferably from about 26% to about 30%.

Preferred anionic surfactant materials useful in the subject compositions include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 24 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of such anionic surfactants are the salts of compatible cations, e.g., sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium, with alkyl sulfates, alkylbenzene or alkyltoluene sulfonates, ethoxylated alkyl sulfates, and other surfactant anions disclosed hereinbelow.

Preferred alkylbenzene and alkyltoluene sulfonates include those with an alkyl portion which is straight chain or branched chain, preferably having from about 8 to 18 carbon atoms, more preferably from about 10 to about 16 carbon atoms. The alkyl chains of the alkylbenzene and alkyltoluene sulfonates preferably have an average chain length of from about 11 to about 14 carbon atoms. Alkylbenzene sulfonates are preferred. Alkylbenzene sulfonate which includes branched chain alkyl is termed ABS. Alkylbenzene sulfonate which is all straight chain is preferred because it is more biodegradable; it is termed LAS and is the preferred anionic surfactant. Alkylbenzene sulfonic acids useful as precursors for these surfactants include decylbenzene sulfonic acid, undecylbenzene sulfonic acid, dodecylbenzene sulfonic acid, tridecylbenzene sulfonic acid, tetrapropylenebenzene sulfonic acid, and mixtures thereof. Preferred sulfonic acids as precursors of the alkylbenzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages from about 11 to about 13 carbon atoms in length. Suitable cations for such alkylbenzene sulfonates include the alkali metals (lithium, sodium, and potassium), ammonium and/or alkanolammonium; preferred are potassium, and especially sodium.

Preferred alkyl sulfates include those with an alkyl portion which is straight chain or branched chain, preferably having from about 8 to about 24 carbon atoms, more preferably from about 10 to about 20 carbon atoms, more preferably still from about 12 to about 18 carbon atoms. The alkyl chains of the alkyl sulfates preferably have an average chain length of from about 14 to about 16 carbon atoms. The alkyl chains are preferably linear. Alkyl sulfates are typically obtained by sulfating fatty alcohols produced by reducing the glycerides of fats and/or oils from natural sources, especially from tallow or coconut oil. Preferred alkyl sulfates include lauryl sulfates, stearyl sulfates, palmityl sulfates, decyl sulfates, myristyl sulfates, tallow alkyl sulfates, coconut alkyl sulfates, C-12-15 alkyl sulfates, and mixtures of these surfactants. Preferred cations for the alkyl sulfates include sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, and triethanolammonium; most preferred is sodium.

Other preferred anionic surfactants include alkylpolyethoxylate sulfates having the formula RO(C2H4θ)χSθ3M wherein R is alkanyl or alkenyl having from about 10 to about 20 carbon atoms, preferably from about 12 to about 16 or 18; X is from about to about 20 on average, preferably from about 1 to about 10, more preferably from about 2 to about 6; and M is a water-soluble compatible cation such as those disclosed hereinabove. The alkylpolyethoxylate sulfates useful in the subject invention are typically condensation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. The alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be synthetic. Preferred cations of such surfactants are potassium, and especially sodium. Specific examples of alkylpolyethyoxlate sulfates include sodium coconut alkylpolyethoxylate (3) ether sulfate, sodium C-12-15 alkylpolyethoxylate (3) ether sulfate, sodium tallow alkylpolyethoxylate (6) ether sulfate, and potassium C-J2-13 alkylpolyethoxylate (1) ether sulfate.

Anionic surfactants include water-soluble salts of the higher fatty acids, or "soaps". This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms.

Other anionic surfactants useful in the subject invention compositions include sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 12 units of ethylene oxide per molecule, and wherein the alkyl group contains from about 8 to about 12 carbon atoms; and secondary alcohol sulfates containing from about 14 to about 18 carbon atoms.

Other anionic surfactants useful in the subject invention compositions include the water-soluble salts of esters of α-sulfonated fatty acids containing from about 8 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1 - sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 10 to about 20 carbon atoms; β-alkoxyalkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyl group and from 8 to about 20 carbon atoms in the alkane moiety; alkylphenol polyethylene oxide ether sulfates, with from about 1 to about 10 units of ethylene oxide per molecule on the average, in which the alkyl radicals contain from about 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid, where fatty acids are derived from synthetic or natural sources; fatty acid amides of a methyl tauride in which the fatty acids are derived from synthetic or natural sources; and β-acetoxy- or β-acetamido-alkane sulfonates, where the alkane has from about 8 to about 22 carbon atoms.

The Silicate Builder

The compositions of the subject invention comprise from about 1 % to about 20% silicate builder, preferably from about 3% to about 17%, more preferably from about 5% to about 15%.

The silicate builder materials are water-soluble silicates which are a mixture of Siθ2 and M2O (M=Na or K), having a ratio of Siθ2: 2θ of from about 1 :1 to about 3.6:1 , preferably from about 1.4:1 to about 3.2:1 , more preferably from about 1.6:1 to about 2.6:1. Such silicates help provide the desired alkalinity for the subject products in use.

Chlorine Bleach

The compositions of the subject invention contain a chlorine bleach material which provides from about 0.003% to about 4% available chlorine based on the weight of the composition, preferably from about 0.01% to about 2%, more preferably from about 0.05% to about 1%, more preferably still from about 0.1% to about 0.5%.

Methods for determining "available chlorine" of compositions incorporating chlorine bleach materials are well known in the art. Available chlorine is the chlorine which can be liberated by acidification of an aqueous solution of hypochlorite ions (or a material that can form hypochlorite ions in aqueous solution) and at least a molar equivalent amount of chloride ions. Numerous materials are known which provide available chlorine.

A conventional analytical method for determining available chlorine is by addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent, such as sodium thiosulfate. Samples of the subject invention compositions are typically dissolved in a water-chloroform mixture to extract any interfering organics, prior to analyzing for available chlorine. An aqueous solution containing about 1% of the subject composition is used to determine available chlorine of the composition.

Many chlorine bleach materials are known, such as disclosed in Mizuno, W.G., "Dishwashing", Detergency: Theory and Test Methods. Surfactant Science Series, Volume 5, Part III, pages 872-878. Chlorine bleach materials useful in the subject invention compositions include alkali metal hypochlorites, hypochlorite addition products, and N-chloro compounds usually containing an organic radical. N-chloro compounds are usually characterized by a double bond on the atom adjacent to a trivalent nitrogen and a chlorine (Cl⁺) attached to the nitrogen which is readily exchanges with H⁺ or M⁺ (where M⁺ is a common metal ion such as Na⁺, K⁺, etc.), so as to release HOCI or OCI^" on hydrolysis.

Preferred alkali metal hypochorite compounds useful in the subject compositions include sodium hypochlorite, potassium hypochlorite, and lithium hypochlorite. Although known as chlorine bleach materials, alkaline earth metal hypochlorites, such as calcium hypochlorite and magnesium hypochlorite, are not preferred for the subject compositions due to poor compatibility of the alkaline earth metal cations with the anionic surfactants.

A preferred hypochlorite addition product useful in the subject compositions is chlorinated trisodium phosphate which is a crystalline hydrated double salt of trisodium phosphate and sodium hypochlorite, which is prepared by crystallizing from an aqueous blend of sodium hypochlorite, castic soda, trisodium phosphate, and disodium phosphate. Chlorinated trisodium phosphate is typically commercially available as chlorinated trisodium phosphate dodecahydrate.

Examples of N-chloro compounds useful as chlorine bleach materials in the subject compositions include trichlorolisocyanuric acid, dichloroisocynauric acid, monochloroisocyanuric acid, 1 ,3-dichloro-5,5-dimethylhydantoin, 1-chloro-5,5- dimethylhydantoin, N-chlorosuccinimide, N-chlorosulfamate, N-chloro-p- nitroacetanilide, N-chloro-o-nitroacetanilide, N-chloro-m-nitroacetanilide, N-m- dichloroacetanilide, N-p-dichloroacetanilide, Dichloramine-T, N-chloro- propionanilide, N-chlorobutyranilide, N-chloroacetanilide, N-o-dichloroacetanilide, N-chloro-p-acetotoluide, N-chloro-m-acetotoluide, N-chloroformanilide, N-chloro-o- acetotoluide, Chloramine-T, ammonia monochloramine, albuminoid chloramines, N-chlorosulfamide, Chloramine B, Dichloramine B, Di-Halo

(bromochlorodimethylhydantoin), N,N'-dichlorobenzoyiene urea, p-toluene sulfodichloroamide, trichloromelamine, N-chloroammeline, N,N'- dichloroazodicarbonamide, N-chloroacetyl urea, N,N'-dichlorobiuret, chlorinated dicyandiamide, and alkali metal salts of the above acids, and stable hydrates of the above compounds.

Particularly preferred chlorine bleach materials useful in the subject compositions are chloroisocynanuric acids and alkali metal salts thereof, preferably potassium, and especially sodium salts thereof. Examples of such compounds include trichloroisocyananuric acid, dichloroisocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, and trichloro-potassium dichloroisocynanurate complex. The most preferred chlorine bleach material is sodium dichloroisocyanurate; the dihydrate of this material is particularly preferred due to its excellent stability.

Optional Ingredients

Optional ingredients which may be incorporated in the compositions of the subject invention include, but are not limited to, the following:

The subject invention compositions preferably comprise at least about 1% phosphorus-containing builder, preferably from about 2% to about 40%, more preferably from about 3% to about 20%, more preferably still from about 5% to about 12%.

Preferred phosphorus-containing builder materials are inorganic phosphate, pyrophosphate, or polyphosphate materials which have the ability to remove metal ions other than alkali metal ions from wash solutions by sequestration, including by chelation or by precipitation reactions. Preferred phosphorus-containing builders include trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate; sodium tripolyphosphate is the most preferred phosphorous-containing builder.

The compositions of the subject invention preferably comprise, as an optional builder, from 0% to about 30% alkali metal carbonate, preferably sodium carbonate, preferably from about 5% to about 20%.

The compositions of the subject invention comprise from 0% to about 60% filler materials such as sodium sulfate, sodium chloride, sucrose, sucrose esters, etc., preferably from about 10% to about 50%, more preferably from about 20% to about 40%. The preferred filler material is sodium sulfate.

The compositions of the subject invention comprise from 0% to about 2% antiredeposition materials such as carboxymethylcellulose, polyethyleneglycol, polyvinylpyrrolidone, polyvinylalchols, etc., preferably from about 0.5% to about 1%. Carboxymethylcellulose is the preferred antiredeposition material. The compositions of the subject invention comprise from 0% to about 5% minor ingredients including, but not limited to, brighteners, perfumes, dyes, etc., preferably from about 0.5% to about 2%.

The compositions of the subject invention comprise from 0% to about 10% moisture, preferably from about 1 % to about 8%, more preferably from about 3% to about 7%.

Processes

The dry particulate compositions of the subject invention can be made by a variety of processes, including dry blending of particulate ingredients and addition of Iiquid ingredients by spraying on and blending in.

Preferred processes for making the subject compositions are well-known processes for making spray-dried detergent products. Typically, surfactant is blended with builders, filler materials, other non-volatile and non-heat sensitive components, and sufficient water to form a slurry which is spray-dried using a standard tower operation. To the dry particulate product thus produced is added the chlorine bleach material and minors via dry blending, spray on, or a combination thereof.

Other preferred processes for making the subject compositions are processes for making agglomerated materials in various mixers. Suitable mixers include high-speed, high-shear mixers such as the Loedige CB®, the Shugi Granulator®, and the Drais K-TTP®, and moderate-speed mixers including plowshare mixers, such as the Loedige KM® and the Drais K-T®. The dry components of the subject compositions are fed to such mixers and intimately mixed. Liquid components can be sprayed into such mixers and be mixed with the dry components therein, or can be sprayed on the mixtures after discharge from the mixer, preferably with an additional blending step.

Examples

The following non-limiting examples exemplify compositions of the subject invention.

Example 1 ingredient Weight Percent

LAS 25

Sodium tripolyphosphate 40

Sodium silicate (ratio 1.6) 7

Lithium hypochlorite 2

Sodium sulfate 18

Carboxymethylcellulose 1

Moisture balance Example 2

Ingredient Weight Percent

LAS 20

Sodium tripolyphosphate 15

Sodium silicate (ratio 2.0) 10

Sodium dichloroisocyanurate dihydrate

1.5

Sodium sulfate 30

Sodium carbonate 20

Moisture balance

Example 3 ingredient Weight Percent

Coconut fatty alcohol sulfate

24

Sodium tripolyphosphate 20

Sodium silicate (ratio 1.6) 3

Chlorinated trisodium phosphate

5

Sodium carbonate 15

Sodium sulfate 28

Perfume 0.8

Moisture balance

Example 4

Ingredient Weight Percent

LAS 28

Tetrasodium pyrophosphate 5

Sodium silicate (ratio 2.35) 14

Sodium dichloroisocyanurate dihydrate

0.5

Sodium sulfate 45

Perfume 0.6

Moisture balance

Example 5

Ingredient Weight Percent

LAS 25

Sodium tripolyphosphate 10

Sodium silicate (ratio 2.0) 6

Sodium dichloroisocyanurate

0.3 Sodium sulfate 43

Sodium carbonate 10

Perfume 0.7

Moisture balance

Example 6

Ingredient Weight Percent

ABS 18

Sodium tripolyphosphate 15

Sodium silicate (ratio 2.0) 8

Potassium dichloroisocyanurate 1

Sodium carbonate 9

Sodium sulphate 45

Moisture balance

Example 7 ingredient Weight Percent

LAS 20

Sodium silicate (ratio 2.0) 10

Sodium dichloroisocyanurate dihydrate

1.5

Sodium sulfate 35

Sodium carbonate 30

Moisture balance

Example 8 ingredient Weight Percent

LAS 28

Sodium tripolyphosphate 5

Sodium silicate (ratio 2.35) 14

Sodium dichloroisocyanurate dihydrate

1

Sodium sulfate 45

Perfume 0.6

Moisture balance

Example 9

Ingredient Weight Percent

ABS 18

Sodium silicate (ratio 2.0) 10

Potassium dichloroisocyanurate 1

Sodium carbonate 10

Sodium sulphate 55 I Moisture balance

The subject invention also involves methods of cleaning cooking or eating utensils by washing them by hand in an aqueous solution or dispersion of the above compositions. Preferred solutions or dispersions of the subject compositions for cleaning cooking or eating utensils are aqueous-based comprising from about 1% to about 8%, preferably from about 2% to about 6%, of the subject compositions, and the balance water.

While particular embodiments of the subject invention have been described, it will be obvious to those skilled in the art that various changes and modifications to the subject invention can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of this invention.

Claims

What is claimed is:

1. A dry particulate detergent and bleach composition comprising:

(a) at least about 18% anionic surfactant;

(b) from about 1 % to about 20% silicate builder; and

2. The composition of Claim 1 wherein the chlorine bleach material provides from about 0.05% to about 2% available chlorine, and is selected from the group consisting of alkali metal hypochlorites, hypochlorite addition products, and N-chloro compounds.

3. The composition of Claim 2 wherein the composition comprises from about 22% to about 40% anionic surfactant, the surfactant comprising a surfactant selected from the group consisting of alkylbenzene sulfonates, alkyl sulfates and alkylpolyethoxylate sulfates.

4. The composition of Claim 3 wherein the composition comprises from about 3% to about 17% silicate builder having a Siθ2: a2θ ratio from about 1.4:1 to about 3.2:1.

5. The composition of Claim 4 wherein the composition comprises from about 24% to about 32% anionic surfactant, the surfactant comprising alkylbenzene sulfonates.

6. The composition of Claim 4 wherein the chlorine bleach material is an alkali metal hypochlorite or a hypochlorite addition product.

7. The composition of Claim 4 wherein the chlorine bleach material is a N-chloro compound.

8. The composition of Claim 7 wherein the N-chloro compound is a chloroisocyanuric acid or an alkali metal salt thereof.

9. The composition of Claim 1 wherein the composition comprises at least about 1 % phosphorous-containing builder.

10. The composition of Claim 4 wherein the composition comprises from about 2% to about 40% phosphorous-containing builder selected from the group consisting of trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.

11. The composition of Claim 8 wherein the composition comprises from about 3% to about 20% phosphorous-containing builder which is tetrasodium pyrophosphate or sodium tripolyphosphate, and from about 5% to about 15% silicate builder having a Siθ2:Na2θ ratio from about 1.6:1 to about 2.6:1.

12. The composition of Claim 4 wherein the composition comprises from about 26% to about 32% anionic surfactant.

13. The composition of Claim 11 wherein the composition comprises from about 26% to about 32% anionic surfactant.

14. The composition of Claim 7 wherein the anionic surfactant consists essentially of LAS.

15. The composition of Claim 13 wherein the anionic surfactant consists essentially of LAS, the phosphorous-containing builder consists essentially of sodium tripolyphosphate, and the chlorine bleach material consists essentially of sodium dichloroisocyanurate.

16. The composition of Claim 4 wherein the chlorine bleach material consists essentially of sodium dichloroisocyanurate.

17. A method of cleaning cooking or eating utensils by washing them by hand in an aqueous dispersion of the composition of Claim 1 , 7, 11 or 15.