SA93130528B1 - detergent formulations - Google Patents

Abstract

Abstract: The present invention relates to a bleaching particulate detergent composition having a high bulk density (at least 700 g/L) comprising one or more detergent compounds, and one or more detergency builders. Includes specific alkali metal P aluminosilicate-maximum aluminum zeolite p MAP zeolite - and a bleach system including sodium perborate monohydrate. The use of MAP zeolite instead of conventional 4A zeolite in this high bulk density formulation substantially improves the storage stability of sodium perborate monohydrate.

Description

Y Detergent Compositions Full Description BACKGROUND OF THE INVENTION This invention relates to a bleaching detergent composition containing crystalline alkali metal silicate alumina on bleach Lay (zeolite) as the detergent building material having a cleaning power of 0616:8600; It also contains 0 sodium perborate monohydrate, sodium perborate monohydrate, calcium ions, sequester Jas. The ability of crystalline alkali metal silicate alumina (zeolite) to make it well known to replace phosphate as a building material with cleaning ability. cdl) of solutions. Zeolite-containing particulate detergent formulations have been widely disclosed in this manufacturing process and sold commercially (Henkel) 1 5777301 in the field. For example, in the British patent in many European countries, Japan and the United States of America. Although there are many forms

AA is known from zeolites, the preferred zeolite for use in detergents is often zeolite 0 its ability to capture oY ions approval of PB) or X die did not find the use of other zeolites has an advantage in being zeolite A + A and calcium dan zeolites are also considered inadequate or slow with a maximum aluminum structure containing the highest possible or theoretically lower ratio of aluminum to silicon; Therefore, its ability to absorb calcium ions -1 in a silicon-to-aluminum ratio of about 51:81 and 7, which generally contains X from aqueous solutions, is substantially greater than that of zeolite-1 with a lower percentage of aluminum (or a ratio of silicon to higher aluminum).‎ ;

P Describes and announces a new zeolite o(Unilever) YA Ve European patent application specifically containing MAP (zeolite©) having the highest percentage of aluminum; or zeolite preferably not greater than 1 ,19; 0.77 low silicon for aluminum, which does not exceed 4A. The material is used to be a building material that is more efficient in terms of cleaning ability than the traditional olay ov. zeolite. About « (Unilever) 07 Ye And 448 YAY European patent applications reveal or polymer citrate auxiliary citrate oly with MAP material Detergent compositions containing zeolite and also containing bleach sodium perborate monohydrate and a substance from which polymer z B v shows cleaning ability MAP and bleach 1151. Formulations containing precursor zeolite

AA contains zeolite Al better than similar formulations It gives additional benefit in MAP powder with zeolite A Now it has been discovered that the replacement of zeolite (g/l and higher) which contains bleach (perborate) Alle bulk detergent; sodium monohydrate; The stability of sodium perborate monohydrate was significantly increased not much lower than MAP during storage and this is considered unexpected because the water content of zeolite

A Water Content of Zeolite General Description of the Invention g/L Yeo This invention provides a particulate bleaching detergent composition having a bulk density of not less than and comprising: 0 (a) one or more active cleaning compounds; (b) one or more detergent building materials with cleaning power containing alkali metal aluminosilicates; and (c) a bleaching system containing sodium perborate monohydrate; in which the ratio of silicon to aluminum is not P and the alkali metal aluminosilicates comprise zeolite eo (MAP) (hereinafter referred to as zeolite 0.77). More than to improve the stability of sodium perborate MAP The other objective of this invention is to use zeolite fom 001 monohydrate in a particulate bleaching detergent composition having an apparent density of not less than liter. Detailed description of the invention © The object of the present invention is a particulate bleaching detergent formulation with a high bulk density containing and a MAP cleaning bleaching system; a detergent building system based on zeolite Blas eld on compounds based on sodium perborate monohydrate. These are the basic elements of this The invention; other detergent ingredients may also be available according to desire and demand. The preferred detergent composition according to this invention includes the following: vo (a) from © to 7180 of one or more compounds with detergent activity; viv

¢ (9) 01 to 7860 of one or more_ge detergent building materials old 5,8 cleaning detergency zeolite-based (MAP) (c) bleaching system included * to 777 Perborate Sodium monohydrate; optionally from 1 to 78 of a precursor bleach (i.e., from which a bleaching compound is formed); and (d) optionally other detergent ingredients up to 7000 by weight” and all proportions are based on the composition of the detergent. The detergent-active compound The detergent compositions of this invention contain, as essential ingredients, one or more compounds with detergent activity ("surfactants") 0. _which may be selected from compounds with soapy and non-soapy anionic, cationic, non-ionic, amphoteric and hybrid 27002 compounds and mixtures thereof. Several compounds with suitable detergent activity are available and are described Completely in scientific journals; for example in: (Surface-active Agents and Detergents) vols 1 and 11 by Schwartz; , Perry Berch. The preferred detergent activity compounds that may be used are synthetic anionic and non-ionic soaps or non-soaps. Anionic surfactants are known Tas to experts in methods. x. Manufacturing in this field. Examples of these substances include alkylbenzene sulfonate 025:; Especially linear alkylbenzene sulfonate compounds with an alkyl chain length of 4-09 carbon atoms Cs-Cis ¢ and primary and secondary alkyl sulphates compounds, especially 0-0; Alkyl ether A) sulphates olefin sulphonates alkyl xylene csulphonates vo dialkyl sulphosuccinates and fatty acid ester sulphonates [2177 acid ester sulphonates]. Sodium salts are generally preferred. z viv o Substances with non-ionic surface activity that can be used include ethoxylates, especially alcohols, primary and secondary alcohol ethoxylates as primary and secondary alcohols

Jase; Mo©-_ aliphatic alcohols ethoxylated conjugated with ethylene oxide CoC, aliphatic specifically Jog per mole of alcohol ethylene oxide mole of ethylene oxide Yo to 1 from to 1 more z©-n© primary and secondary aliphatic alcohols united with ethylene oxide at a rate of 1 mole of ethylene oxide per mole of alcohol. Also important are the non-ionic surfactants that are not united with oxide and ortho- Alkylpolyglycosides Alkyl polyglycosides (Ji ethylene, for example, as described in the European patent application <O-alkanoyl glucosides Alkanoyl glucosides (Unilever) 77 cubic meters 0 depends on the choice of the compound with the cleaning activity (a substance with surface activity) and the amount of its presence depends on the intended use of the detergent formula: you may choose a different surfactant (surfactant material), as it is well known to experts in the composition of these compounds for hand washing products and for products intended to be used in different types of washing machines. The washing. The intended Aled and also the presence of the total amount of the surfactant depends on the use Vo by weight. 7460 Go for the detergent composition; but it generally ranges from © to 770 by weight and is preferred Detergent formulations suitable for use in most automatic washing machines generally contain either anionic non-soap surfactants or non-ionic surfactants or: combinations of the two in any ratio and optionally with soap. Detergent Building Material System with Cleaning Power 0 The detergent composition of this invention also contains one or more detergent building materials with cleaning power. The appropriate total amount of detergent building material varies in capacity

CaM TA to 01 cleaning in formulations from

MAP The cleaning power building material system of the formulations of the present invention is based on zeolite and optionally in combination with one or more complementary building material cleaners. The ve present in the formulation may appropriately range from © to 770 by weight, most preferably from MAP Zeolite to 7460 by weight.

Yev

1 The preferred alkali metal aluminosilicates contained in this invention consist entirely of zeolite MAP in the form of (SA : zeolite MAP) zeolite MAP (Maximum Zeolite Aluminium© content) and its uses in detergent formulations are described and declared In European patent application (Unilever) 784 170 it is defined as an alkali metal aluminosilicate of type zeolite© in which the ratio of silicon to aluminum is not higher than FY and preferably within the range 0.4 to NY For special purposes, a MAP zeolite with a silicon-to-aluminum ratio of not less than 09 and a MAP zeolite with a silicon-to-aluminum ratio of not higher than 0.17 is particularly preferred. MAP generally has a calcium-binding capacity of not less than Vou mg of CaO per gram of anhydrous aluminosilicate, as measured by the standard methods described in UK Patent (Yo) 77; (Henkel) 1 also described as Method 1” (Method I) in European Patent Application (Unilever) 784 1760 . The binding capacity of 1 calcium is usually at least 160 mg [CaO g] and may be as high as 171 mg [CaO g. MAP zeolites generally also have an “effective calcium binding capacity” measured as described under (Method IT) IT in European patent application “(Unilever) 84”. Vo which is at least VEO mg [CaO g] and preferably at least 0 mg [CaO g. Y. Although the zeolite Jie MAP the rest of the zeolites contain water from the addition of water hydration and for the purposes of this invention; It expresses the amount of zeolite and its percentage generally used in this invention according to the concept of non-aqueous materials (does not contain water). The amount of water contained in MAP hydrated zeolite at ambient temperature and humidity is usually about 0 by weight. Yev

Y

MAP cule il particle size The preferred particle size for use in this invention is the specially finely divided MAP zeolite to 5.0 μm 021 such that it has a wall (as you will later know) within the limits of the range of 01 micrometers to 1.4 micrometers and the most preferred from 7.0 to 1.4 ST and the preferred by weight of particles with a smaller diameter than the previous number 750 The quantity is "mol denotes that “wal”; etc. Particularly preferred material <"dgg" mentioned; There are also corresponding quantities of μm. 1 are those with a wall of less than μm; In addition to the less than, the different methods of measuring particle size are known methods and they all give small differences in the results. In the current specifications, the distribution of particle size and average values (by weight) supplied to (brand (Malvern Mastersizer) were measured by the Malvern Mastersizer device (quoted), for example - after dispersing it in demineralized water (distilled water) and exposing it to cae £0 commercial) using a 0.01 minute lens for ultrasonification for ultrasound Not only the average size of the MAP particle but not essential The zeolite may have cada and in a small way but may It also contains a low percentage or may even be essentially free of large particles. It may therefore be advantageous to distribute the particle size to at least 7460 wt preferably 1 µm and at least 7805 wt 01 be at least 7955 wt having a size less than and preferably at least 7950 wt smaller than + µm; and at least 780 by weight and preferably at least 7805 by weight less than © μm. Other (builders) building materials for the detergent as desired; In combination with an organic detergent building material or MAP zeolite Ye

A is another inorganic. anyway; It is preferable not to have significant amounts of zeolite. The inorganic detergent building materials that may be present in the formula contain carbonate crystallisation seeds, as desired, in association with sodium carbonate crystal seeds, as shown in the British patent 08101070 carbonate For calcium carbonate It includes _ organic detergent building materials that may be present in (Unilever) €YY de. vo Polyacrylates “Jie polycarboxylate polymers Composition on cacrylic/maleic copolymers Acrylic/maleic copolymers polyacrylates ev

A

quot; monomeric citrates monomeric polycarboxylate tacrylic phosphinates phosphinates mono-glycerol coxydisuccinates oxydisuccinate gluconates gluconates ccitrates mono-, di- and trisuccinates Aldi 8170©01 Malones Sy Jie SS ccarboxymethyloxysuccinates | Dihydroxyethylimino diacetates ddipicolinates Picolinates AS ccarboxymethyloxymalonates 0 alkyl- and malonates July Alkyl- chydroxyethyliminodiacetates sulphonated fatty acetates succinates and alkenylmalobates This list is not intended to It is inclusive of all materials. .810 salts It is preferred that the presence of both organic and inorganic detergent building materials be in the form of an alkali metal salt; particularly in the form of sodium salt. -0 MAP salts and detergent building materials include the preferred complement for use in conjunction with zeolites which are sodium citrate and more specifically sodium citrate ccitric acid salts by weight. Suitable for use in quantities from 9 to 7780 by weight, preferably from © to

EEA YAY A description and declaration of this detergent building material is found in the European patent application: (Unilever) 0 “polycarboxylate polymers. Polycarboxylate polymers are also preferred and used in the form of maleic maleic / acrylic and with the specification of more copolymers than acrylic By weight of detergent formulation; 70 to 1 suitable in quantities ranging from: (Unilever) ©+Y 676 European patent calla. The composition of this detergent builder in bleach system (and system 0 contains Detergent compositions according to the present invention on a bleaching system which is based on inorganic Jie inorganic persalt sodium perborate This compound is a particularly effective bleaching agent due to its high content of active oxygen monohydrate and its rate of dissolution The presence of sodium perborate monohydrate is appropriately in an amount from © to Ive by weight, preferably from 01 to 778 by weight; on the basis of detergent composition. viv |

q and according to desire, the ovarian system may also contain a substance from which the ovary is formed (a precursor. Ovarian base material) which are peroxyacid percursors and the substances that make up the peroxy acid bleach are known and described at length in scientific publications; For example, in patents

° BRITISH NUMBERS AV Yo ATE YAA (ATT GAA N.L. Yor COMPLETE E), German Patent 971 oF 7317 & European Patent Applications 0577 VAS 070 04) (IVE 7” & US Patent No. 57,779 7, US Patent No. 2,777,887 US Patent No. 54,178,446 US Patent No. 9,74 and US Patent No. 5,175,797.

“peroxycarboxylic acid percursors and preferred bleaching primers are acid primers 1, peracetic acid percursors, and more specifically, peroxybenzoic acid percursors -peroxycarboxylic acid percursors carboxylic

One type of particular interest is made by means of bleach substrates replaced with ammonium

ve quaternary ammonium- and phosphonium-substituted, for example, as described in US Patent No. 5,791,016 and US Patent No. £,Y4V,Vov (Lever Brothers Company) and EP Nos. YAY 784 and 779 (Unilever) 771 The preferred peroxy acid bleaching primer from this group is NNN-Y trimethylammonium ethyl sodium-;-sulfophenyl:

2-N,N,N-trimethyl ammonium ethyl sodium-4-sulphophenyl | Chloride carbonate | cholyl-p- also known as cholyl-c-sulphophenyl carbonate SPCC carbonate chloride (CSPC) sulphophenyl carbonate

Other examples of preferred peroxy-acid bleaching primers for use in the present invention include: Yo sodium;- SBOBS sodium 4-benzoyloxybenzene sulphonate; Yey

0 N,N,N',N'-tetracetyl ethylenediamine; sodium-1methyl-7-benzoyloxybenzene-; = sulfonate; sodium 1-methyl-2-benzoyloxybenzene-4-sulphonate; 2 sodium 4-methyl-3-benzoyloxybenzoate; ° trimethylammonium toluyl oxybenzene sulfate; trimethylammonium toluyloxybenzene sulphate; sodium nonanoyloxybenzene sulphonate; EC numbers YAY 76 t 070 0707 £0A TAT sq 16 (Kao) The presence of ovarian precursors is appropriate in amounts from 1 to 78 wt.; the preferred JY oe ae is 26 wt. Particulate bleaching detergent formulations having a volumetric density of at least 701 g/L and containing a detergent building material system including MAP zeolite and a bleaching system including peroxy bleach compound and bleach base material are the object of our accompanying pending application on the same date (case 03488 7 Other ingredients that can be found in the detergent formulations of this invention include sodium silicate, dale materials for dust re-deposition, Jie antiredeposition, cellulosic polymers, fluorescers, inorganic salts inorganic Jie salts sodium sulfate sulphate 0070-500; lather control agents or lather boosters as appropriate, vo dyes and fragrances. This list is not intended to be inclusive of all other ingredients. B

11 bulk density The bulk density of the particulate detergent formulations of this invention is not less than 7090 g/l g/l. It is preferable that it not be less than 3 Preparation of detergent formulations Preparation of particulate formulations of this invention By any suitable method for the production of powder (Se °

Ale with bulk density slurry ol sill spray-drying One of the suitable methods includes spray drying hid and any MAP building materials of non-heat sensitive ingredients; Compatible” including Zeolite Powder Densifying Least Part of Compounds with Detergent Activity and Jey Thickening Other; batch or base produced in a high speed granulator/mixer intermittently or continuously 0 and then sprayed or dosing, by continuous high-speed mixer/granulator, of those ingredients unsuitable for the process by means of loose dough and containing additional postdosing: sodium perborate monohydrate and any other bleaching ingredients. Particularly preferred; It is possible to omit the spray drying step completely; og al and in the method of high bulk density directly from the raw materials base powder and the base powder 1 constituent of it is prepared; By mixing and granulating in a high speed granulator/mixer; Then doses of bleach and other ingredients are added, as is known in the spray-drying/turret-drying method. Processes using high-speed granulators/mixers have been described in Unilever patent applications 7 470 European invention 07 0740 4 Enf Nama Ho © Examples in which parts and percentages are expressed Adil This invention is also illustrated by examples by weight unless otherwise indicated. The examples defined by numbers are those according to the invention while the examples defined by letters are comparative examples. The ones used in the examples by a method similar to that described in the examples MAP zeolites were prepared Yo: silicon to (Unilever) A 784 1768 to ¥ of the 1 European patent from the neighborhood

1" in it and measured by Malvern Mastersizer (dsp) and the particle size was NY x aluminum in it . µm +, A (Malvern Mastersizer) (trademark) 7 Wessalith powder used is A The zeolite was: Degussa The anionic surfactant used was primary coconut alcohol sulfate The non-ionic surfactant was Philippine Refining Co. from cocoPAS which is an ICT and 3 of AT (brand) Synperonic used is and “mol of ethylene oxide. 1 alcohols conjugated with ethylene oxide in a row at a rate of ,2-5 (1) Example for comparison 1 Example Detergent base powders were prepared according to the compositions mentioned later (part by weight), by 1 (trademark) granulator / intermittent high-speed mixer. Fukae by mixing and granulating in a device 1 89.0 8.0 Coconut alcohol sulfate CocoPAS |

Ye 7,01 380 Non-ionic 3 ethylene oxide surfactant surfactant (non-aqueous *) - for 4A zeolite - Yo (non-aqueous *) Zeolite: Yo - Sodium Carbonate © 'on on Critical Micelles for Servactant (3S 5) SCMC

OY LY is a fluorinator

Le aXe CO Humidity (nominal) 1, En £A,41

AMA AA Bulk Density (g/L) vo Zeolbit was used in aqueous form; However, the quantities given are for non-aqueous (dry) materials; The hydrogenation water is *. Within the quantities shown for total humidity. (This part located directly below the table) D sold

The actual amount of moisture in the base powders was determined by measuring the weight loss after heating to Bgl Yo for 1 hour; It was found as follows: Humidity (7 by weight) AT 1.05 for Example 1 and Comparative Example A, respectively. Therefore, MAP zeolite base powder has a slightly higher moisture content. 0 Then prepare powder samples by mixing © 1.7 g of sodium perborate monohydrate with AYO g of each base powder. Therefore each powder contains 787.50 wt base powder 717.91 5 wt sodium perborate monohydrate. Products were stored in open vials at YYC - 7970RH. Storage stability was evaluated by removing samples at intervals of time and measuring its content of residual 0 oxygen by titration with potassium permanganate, and the results were expressed as percentages of the initial value and were as follows: Storage time (days) 1 1 0 0 1 va zero Ve

Ao, ¢ 47 7 “14, AYN \ s ovo LY YA 7. Thus, the best stability of sodium perborate monohydrate was shown in the powder containing MAP zeolite although its moisture content was higher.

Claims (1)

Ye Protection Elements Density Jd particulate bleaching detergent composition A particulate bleaching detergent composition 1-1 includes the following: fl g/1001 No less than apparent surface activity x surface activity ld (a) from © to 770 by weight of one or more v “surfactant compounds ¢ builders capacity to 7280 by weight of one or more of the detergent building materials 01 a (b) of and alkali metal aluminosilicate cleaning alkali metal aluminosilicate 1 comprising of © to 775 wt sodium perborate bleach system (c) bleach system v 78 wt (AY) and optionally sodium perborate monohydrate monohydrate A “bleach precursor from bleach 4; 2001163 has a silicon content that is not P where alkali metal aluminosilicates contain zeolite 1 to 0 μm; zeolite is present 101 and a wool particle size of MAP zeolite 0.77 is greater than 1 by weight; all percentages are based on 7540-19 mentioned in an amount ranging from MAP VY to detergent formulation. With a ratio of silicon to aluminum MAP where zeolite 1? - Detergent composition as of claim 1,#1 not greater than Y having a ratio of silicon to aluminum MAP Detergent composition as of claim 7; Where Zeolite -* 1 NY is not greater than Y A which is substantially free of Zeolite 1 Detergent Composition- as of claim 4 -0 of which Bale Detergent Composition of Claim 1 is formed; which also includes an effective amount of -# 1 bleach precursor Y CA Bleach 8000 g/ 8000 as per claim 1; It has a bulk density of at least 1-1 5 dS 1 viv