HU217991B - Granular bleaching or cleaning compositions containing aluminosilicates and zeolite p containing exchangeable cations - Google Patents

Abstract

The particulate detergent, bleaching or cleaning composition of the present invention comprises crystalline aluminosilicate comprising a moisture sensitive bleaching component and exchangeable cations, wherein the aluminosilicate contains at least 5% by weight of exchangeable cations of ammonium and / or lithium, and / or lithium. The invention further relates to a zeolite of the aP type with a silicon: aluminum atomic ratio (MAP type) of up to 1.33, which contains exchangeable cations, in which at least 5% by weight of the exchangeable cations are ammonium ions and / or lithium ions and / or hydrogen ions. ŕ

Description

The present invention relates to a granular detergent, bleaching or cleaning composition comprising a crystalline aluminum silicate (zeolite) comprising a moisture-sensitive bleaching component and replaceable cations. More particularly, the present invention relates to a cleaning composition comprising inorganic persalts as bleaching ingredients, including sodium percarbonate, organic or inorganic peroxyacids, and bleaching precursors. The invention further relates to a P-type (MAP type) zeolite having up to 1.33 silicon aluminum atoms and containing exchangeable cations.

The ability of crystalline aluminum silicates (zeolites) to bind calcium ions from aqueous solution by an ion exchange mechanism has led to the known replacement of phosphates used as detergent ingredients. Many granular detergent formulations commercially available in Europe, Japan, and the US contain zeolites.

Although many crystalline forms of the zeolite are known, zeolite type A is always used for detergents, preferably always in sodium form.

Detergent formulations containing zeolites are disclosed, inter alia, in EP 456 515A, EP 38 591 A, EP 21 491A, EP 87 035A, US 4 604 224 and CA 1 072 853. Zeolites A, X, Β (P) and Y are known. and a number of general formulas for the range of possible cations, however the most preferred cation is sodium and all specific teachings refer to zeolites in sodium form.

Sodium percarbonate in bleaching and detergent formulations is a well-known and widely known bleaching ingredient in the literature, although its use in commercial products has declined in recent years in favor of sodium perborate. In the presence of moisture, sodium percarbonate is less stable than sodium perborate and has been difficult to stabilize in detergent powders for a long time. This difficulty becomes particularly acute when sodium percarbonate is introduced into a detergent powder containing a large amount of unbound water, where it is inactivated during storage. This is particularly true for powders containing zeolites, since the zeolites contain large amounts of relatively mobile water.

This problem is discussed in GB 2 013 259A, which proposes, as one solution, the use of a zeolite in which the sodium cations are partially replaced by calcium or magnesium ions. This measure improves the stability of sodium percarbonate, but at the expense of the effectiveness of the detergent builder (calcium and magnesium ion exchanger).

Another solution to the problem of the stability of percarbonate in granular zeolite-containing detergent formulations is described in EP 522 726A. Accordingly, the standard type A zeolite is replaced by a type P zeolite (MAP type) having a silicon: aluminum ratio of up to 1.33 as described and claimed in EP 384 070A. The use of such a zeolite significantly improves the storage stability of sodium percarbonate.

Similar improvements in storage stability have been observed for sodium perborate monohydrate (EP 552 053A), bleach precursors (EP 552 054A), peroxyacids (WO 94/13773).

The invention is based on the discovery that the storage stability of sodium percarbonate and other moisture sensitive ingredients, particularly in zeolite-containing detergent and cleaning compositions, can be significantly further improved by the use of zeolites in which the sodium ions are at least partially replaced by other cations. This is surprising because the moisture content of the ion-exchanged materials is generally not less than that of the corresponding sodium-containing materials and, according to the invention, the zeolites are used in a fully hydrated form in an environment where the mobile water content is not controlled. Improvement was observed in both A and MAP zeolites.

EP 364 184A discloses non-aqueous cleaning agents containing dispersed aluminosilicate grains wherein the aluminosilicate is inactivated by treatment with ammonia or a substituted ammonium compound and then heated to reduce the water content to less than 24% by weight. This treatment reduces the decomposition of bleach precursors in the liquid product, such as tetraacetyl ethylenediamine aluminum silicate. In contrast to the present invention, 364 184A relates to a medium (a non-aqueous liquid) in which the water content is strictly limited and controlled and partially dehydrated aluminum silicates.

Accordingly, the present invention provides a granular detergent, bleaching or cleaning composition comprising crystalline aluminosilicate comprising a moisture sensitive bleaching component and exchangeable cations and containing at least 5% by weight of exchangeable cations of aluminum silicate with ammonium and / or lithium. , and / or hydrogen ions.

More particularly, the present invention is a particulate bleaching, detergent composition comprising an organic detergent surfactant, a moisture-sensitive bleaching ingredient, and crystalline aluminum silicate, wherein the aluminum silicate is as defined in the preceding paragraph.

The present invention further provides a novel substance of the type Zeolite P having a silicon: aluminum atomic ratio up to 1.33, preferably up to 1.15, most preferably up to 1.07, containing zeolite exchangeable cations containing at least 5% by weight of ammonium ions and / or lithium ions. and / or hydrogen ions.

The composition of the present invention comprises two basic ingredients, aluminum silicate and a moisture sensitive component.

The ion-exchanged zeolite

Crystalline aluminosilicate (zeolite) is required as an essential ingredient for the compositions of the present invention, wherein the exchangeable cations are at least partially ammonium ions and / or lithium ions and / or hydrogen ions.

HU 217 991 Β

Such a zeolite is readily prepared by ion-exchange from zeolite in sodium form, and for simplicity is referred to herein as an ion-exchanged zeolite, although in principle the invention includes the use of directly synthesized non-ionic zeolites in non-sodium form, .

Zeolites prone to ion exchange can be expressed by the following general formula (II):

M _x (SiO ₂ ) _y (A 10 ₂ ) _x · z H ₂ O (II) in which M represents a monovalent cation. The ratio of silicon to aluminum (y: x) can vary, as can the amount of hydrate water.

Partially ion-exchanged zeolite can be represented by the general formula (III):

MUM ^ ySiO ^ / AlOAz H ₂ O (III) wherein M ¹ and M ² are two different interchangeable monovalent cations.

The degree of ion exchange (mole) as a percentage of the cation M ¹ is given by:

^ 100th

The x x and x 'values can be determined by standard analytical techniques such as atomic absorption spectroscopy.

Zeolites used in this invention, the M ¹ cations are ammonium, lithium and hydrogen. Zeolites in the form containing hydrogen ion and ammonium ion are preferred, especially zeolites in the form containing hydrogen ion. It has been found that potassium ions from strong bases have the opposite effect, since the zeolites in the potassium-containing form reduce the stability of the moisture-sensitive constituents relative to the corresponding sodium-containing forms.

Preferably, the M ² cation is a sodium ion.

When M ¹ is a hydrogen ion, x 'is conveniently determined as the difference between the concentration of aluminum (x) and the concentration of the second cation (M ² ).

The zeolite may be in any crystalline form suitable for use as a detergent. According to the above, type A zeolite is the most commonly used detergent. Although it is known in the art to use zeolites X, Y and P (B), in practice they are not favorable due to their low or too low calcium uptake.

Zeolite type A has the advantage of having the maximum possible aluminum to silicon atom ratio (or a possible minimum silicon to aluminum atomic ratio of 1.0), so that it has an inherently higher calcium ion uptake capacity in aqueous solution than zeolites X, Y and P, which generally contain less aluminum (or which have a higher ratio of silicon to aluminum).

According to the above, in a preferred embodiment of the invention, the partially or completely ion-exchanged zeolite is a type A zeolite.

Alternatively, and most preferably, the partially or fully deionized zeolite may be the MAP type zeolite described and claimed in EP 384 070B, discussed above.

This is a P-type zeolite containing a maximum amount of aluminum, i.e. a P-type zeolite of up to 1.33, preferably up to 1.15, more preferably up to 1.07 Si: Al. The zeolite MAP has many advantages over the zeolite A; Among other things, it improves the stability of sodium percarbonate and many other bleaching ingredients, even in the form of sodium.

Ion-exchanged zeolites are known from the literature [D. W. Breck and E. M. Flanagan, Molecular Sieves, Soc. Chem. Ind. (London), 1968, 47-61. US 4,346,067 discloses ammonium-exchanged zeolites, EP 223,396A discloses hydrogen-exchanged zeolites, which are useful catalysts in hydrocarbon conversion reactions.

However, MAP-type zeolites in ion-exchanged form are new substances and therefore require protection.

Degree of ion exchange

In order to take full advantage of the improved moisture stability of the ingredients, the zeolites are desirably in deionized form at least 5% by weight, preferably at least 10% by weight, more preferably at least 20% by weight. Higher levels of ion exchange do not result in further improvement, but the benefit is maintained.

Accordingly, at least 5% by weight, preferably 10%, more preferably at least 20% by weight of the zeolites used in the present invention are in deionized form.

It has been found that good results can be obtained when 10-50% by weight, especially 20-50% by weight of the zeolite type A is in deionized form, while for the zeolite type MAP, 10-90% by weight, especially 20-90% by weight ion-exchanged form leads to good results.

Values close to said lower limit are particularly applicable to zeolites exchanged for ammonium ion. Suitable limits for other cations are not necessarily the same as those set forth above, but can be readily determined by one of ordinary skill in the art using the procedures described in the Examples.

Preparation of ion-exchanged zeolite

The ion-exchanged zeolite may conveniently be prepared by immersing the appropriate sodium-containing zeolite in an aqueous solution of the desired cation salt, such as an ammonium or lithium salt.

Zeolites exchanged for hydrogen ions can likewise be prepared by immersion in an aqueous solution of a strong acid such as hydrochloric acid.

The degree of ion exchange expressed as a percentage can be controlled by varying the concentration of the salt or acid as described in detail in the literature [D. W. Breck et al., JACS 78, 59-63. (1956)].

Compositions of the invention

The detergent, bleach or detergent compositions of the present invention comprise a crystalline aluminosilicate (zeolite) detergent forming system and at least one moisture-sensitive alk

HU 217 991 Β also. Although the invention is applicable to any moisture sensitive ingredients, the focus of the initial research phase was on the moisture sensitive bleach ingredients.

Moisture-Sensitive Bleaching Ingredients Moisture-sensitive bleaching ingredients include peroxy compounds such as inorganic or organic peracids and peroxyacids and bleach activators (bleach precursors).

Inorganic Persians

Inorganic persalts include alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. The moisture-sensitive inorganic persalts to which the invention is particularly applicable include sodium perborate monohydrate and especially sodium percarbonate.

Inorganic persalts may preferably be used in combination with a bleach precursor or bleach activator. Bleach precursors themselves may be sensitive to moisture, and thus their stability can be improved by the present invention.

The compositions of the present invention may also contain a stabilizer (heavy metal complexing agent) for the bleaching agent. Suitable stabilizers for bleaching agents include ethylenediamine tetraacetate (EDTA) and polyphosphonates such as Dequest (EDTMP).

Bleach precursors

Preferred bleach precursors are peroxycarboxylic acid precursors, in particular peracetic acid and peroxybenzoic acid precursors and peroxycarboxylic acid precursors.

Suitable peroxyacid bleach precursors for use in the present invention include:

- Ν, Ν, Ν ', Ν'-tetraacetyl ethylenediamine (TAED),

- 2- (N, N, N-trimethylammonium) ethyl-sodium-4-sulfophenyl carbonate chloride (SPCC), also known as colyl-p-sulfophenyl carbonate (CSPC),

- sodium nonanoyloxybenzenesulfonate (SNOBS),

- sodium 4-benzoyloxybenzenesulfonate (SBOBS),

- sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS), and

- glucose pentaacetate (GPA).

peroxyacids

Peroxy acids useful in the present invention may be organic or inorganic compounds.

Organic peroxyacids can be represented by the general formula (IV):

SHE

II

HOOCC'R-Y (IV) having the formula

R is a C 1 -C 12 alkylene or substituted alkylene group optionally having an internal amide bond or an optionally substituted phenylene group, and

Y is hydrogen or halogen, alkyl, aryl, imido-aromatic or non-aromatic, carboxylic or percarboxylic acid, or quaternary ammonium.

Typical monoperoxy acids useful in the compositions of the invention include: i) peroxybenzoic acid and ring-substituted peroxybenzoic acids such as peroxy-α-naphthoic acid; iii aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxyl lauric acid, peroxy stearic acid, and

Ν, Ν'-phthaloylamino-peroxy-caproic acid (PAP);

iii) 6-octylamino-6-oxoperperoxyhexanoic acid.

Typical diperoxy acids useful in the compositions of the present invention include:

iv) 1,12-diperoxydodecanedioic acid (DPDA);

v) 1,9-diperoxy-azelaic acid;

vi) diperoxy-brazilic acid, diperoxy-sebacic acid and diperoxy-isophthalic acid;

vi i) 2-decyldiperoxy-butane-1,4-dione acid;

viii) 4,4'-sulfonyl-bis-peroxybenzoic acid; and ix) N, N'-teretaloyl di (6-amino-peroxycaproic acid), also known as N, N'-di (5-percarboxypentyl) terephthalamide (TPCAP).

bleaching

The composition of the invention may include, inter alia, a detergent additive consisting wholly or predominantly of aluminum silicate detergent and at least one moisture sensitive bleaching ingredient.

This type of additive may be used in conjunction with a conventional product in cases where high water hardness and / or high degree of contamination require a higher than usual detergent forming and / or bleaching ability.

Such an additive may also form part of a building block system (EP 419 03 6A), in which case it is used in combination with a low detergent and / or bleach-free base detergent powder.

detergent

The composition of the present invention may also be a particulate detergent composition suitably containing the following ingredients:

(a) at least one organic detergent surfactant,

b) a detergent builder comprising crystalline aluminosilicate as defined above,

(c) at least one moisture sensitive component; and

(d) where appropriate, other detergent ingredients.

The detergent compositions of the present invention comprising moisture-sensitive bleaching ingredients may suitably contain the following ingredients:

(a) at least one organic detergent surfactant,

b) a detergent builder comprising crystalline aluminum silicate as defined above,

(c) a bleaching system containing at least one moisture sensitive component; and

(d) where appropriate, other detergent ingredients.

Preferred detergent compositions of the present invention may contain the following ingredients in the ratios given:

a) 2-60% by weight of at least one detergent surfactant,

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(b) 10% to 80% by weight of at least one detergent builder comprising partially or completely deionized zeolite,

(c) a bleaching system containing from 5% to 40% by weight of a moisture sensitive bleach component; and

d) optionally up to 100% by weight of other detergent ingredient (s).

The moisture-sensitive bleaching ingredient as defined above may be perso, bleach precursor or peroxyacid, more preferably sodium percarbonate or peroxyacid.

Detergent surfactants

The detergent compositions of the present invention contain as an essential ingredient at least one detergent active compound (surfactant), which may be soap (s) and non-soap anionic, cationic, nonionic, amphoteric or inner salt detergent active compound (s) or their mixture (s). Many suitable detergent active compounds are commercially available or are known in the art (Schwartz, Perry and Berch, Surface-Active Agents and Detergents, I and II). Volume].

Preferred detergent active compounds are soaps and synthetic non-soap anionic and nonionic compounds.

Anionic surfactants are known to those skilled in the art. Examples of such compounds are alkyl benzene sulfonates, especially C 8 -C 15 straight alkyl alkyl benzene sulfonates; primary and secondary alkyl sulfates, especially C 12 -C 15 primary alkyl sulfates; alkyl ether sulfates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulfosuccinates and fatty acid ester sulfonates. Sodium salts are generally preferred.

Nonionic surfactants which may be used include primary and secondary alcohol ethoxylates, in particular on average per mole of alcohol.

C8-20 primary and secondary aliphatic alcohols ethoxylated with 1 to 20 moles ethylene oxide, in particular 1-10 moles ethylene oxide ethoxylated 9-10 primary aliphatic alcohols.

Also important are non-ethoxylated nonionic surfactants such as alkyl polyglycosides, O-alkanoyl glycosides described in EP 423 968A, and polyhydroxyamides.

The choice of detergent compound (surfactant) and the amount thereof will depend on the intended use of the detergent composition. As known to those skilled in the art of formulating these types of formulations, different surfactant systems may be selected for handwashing and different types of product for use in washing machines.

The total amount of surfactant present will also depend on the intended end use, although generally

In the range from 2 to 60% by weight, preferably from 5 to 40% by weight.

Most detergent compositions suitable for use in most automatic washing machines generally contain anionic non-soap surfactant or nonionic surfactant or any combination of the two, optionally with soap.

The detergent make up system

The detergent compositions of the invention also contain at least one detergent builder. Suitably, the total amount of detergent-forming agent in the composition is in the range of 10-80% by weight.

The detergent builder system of the compositions of the present invention is based on a zeolite, optionally in combination with one or more additional detergent builders.

The amount of zeolite present is suitably 5-60% by weight based on anhydrous materials, more preferably 15-40% by weight (corresponding to 6-75% by weight based on hydrated materials, preferably 19-50% by weight).

The zeolite may optionally be used in combination with other inorganic or organic detergent builders. As inorganic detergent builders it can be used in conjunction with seed germinating sodium carbonate, optionally calcium carbonate, as described in GB 1 437 950. Examples of organic detergent builders include polymers of the polycarboxylate type. such as polyacrylates, acrylic / maleic copolymers and acrylic phosphinates; monomers of polyhydric carboxylates such as citrates, gluconates, oxysuccinates, mono-, di- and trisuccinates of glycerol, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, and succinates, and salts of sulfonated fatty acids.

Preferred additional detergent ingredients for use with the zeolite include, inter alia, citric acid salts, especially sodium citrate, in an amount of from 3 to 20% by weight, more preferably from 5 to 15% by weight. The combination of MAP zeolite citrate as a detergent-forming system can be found in EP 448 297A.

Polycarboxylate type polymers, in particular acrylic acid / maleic acid copolymers, which are suitably present in the detergent composition in an amount of from 0.5 to 15% by weight, in particular from 1 to 10% by weight, are also preferred. The use of MAP type zeolite polymer with detergent builders is described in EP 502 675A.

The bleaching system

As mentioned above, the detergent compositions of the present invention may comprise a bleach system comprising at least one moisture sensitive ingredient. The bleaching system may generally comprise a peroxy-type bleaching agent, such as an inorganic or organic peracid, optionally together with a bleach activator (bleach precursor) to increase the bleaching effect at low wash temperatures, or an inorganic or organic peroxyacid. A stabilizer for the bleach (heavy metal complexing compound) may also be present.

Preferred inorganic persalts are sodium perborate monohydrate and sodium percarbonate. As stated above, sodium percarbonate is particularly sensitive to moisture and therefore the present invention has particular advantages.

Sodium percarbonate or other persalts in the detergent compositions of the present invention are present in total

Suitably they may be present in an amount of 5 to 30% by weight, preferably 10 to 25% by weight, based on the weight of the compound.

Suitably the bleaching agent cursors are used in an amount of 1 to 8% by weight, preferably 2 to 5% by weight.

Organic or inorganic peroxyacids are usually used in an amount of 2 to 10% by weight, preferably 4 to 8% by weight.

Other ingredients

Other substances present in the detergent compositions of the present invention include, but are not limited to, sodium silicate; antifouling agents such as cellulose-type polymers, fluorescent additives, inorganic salts such as sodium sulfate, antifoaming agents or antifoaming agents, pigments and fragrances for the intended purpose of the composition.

Preparation of detergent compositions

The granular detergent compositions of the present invention may be prepared by any suitable method.

One suitable method is by spray drying the compatible heat-insensitive ingredients, including the zeolite, any other ingredient, and at least a portion of the detergent-active compound, and then the non-processable ingredient, including sodium percarbonate, and any other bleach. the ingredient is subsequently sprayed or dispensed. It is not difficult for one skilled in the art of detergent formulation to determine which ingredients should be included in the slurry and which should not.

The compositions of the present invention may be prepared by tower-free processes, such as dry mixing and granulation, or by so-called "mixed" processes, which include a combination of tower or non-tower processes.

The advantages of the present invention take the form of powders of high density, such as at least 700 g / l in bulk. Such powders may be prepared either by post-compaction of the spray-dried powder or by non-tower processes such as dry mixing and granulation. In both cases a high speed mixer / granulator is preferred. Processes using a high speed mixer / granulator are described, inter alia, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A.

The invention will now be illustrated by the following examples, in which, unless otherwise stated, the data given in parts or% is by weight. The numerical examples are examples of the invention, while the numerical examples are for comparison.

- Examples 14

Comparative Examples A and B

Preparation of ion-exchanged zeolites

Example 1

Production of zeolite type A exchanged for ammonium ion

Type 4A sodium zeolite powder (trade name Wessalith P, manufactured by Degussa) was partially converted to ammonium ion-exchanged zeolite as follows.

150 g of hydrated zeolite type 4A in sodium form were suspended in 1 L of 0.2 M ammonium sulfate (adjusted to pH 9 with ammonium hydroxide) for 1 hour at 60 ° C. The slurry was then filtered and the cake was resuspended in a further 1 L of fresh ammonium sulfate solution. Repeating this operation, we performed a three-step procedure. The zeolite was finally filtered, washed with deionized water and dried in a 100 ° C oven. The dried zeolite was ground in a mortar and stored under ambient conditions for several days for complete hydration.

The fully ion-exchanged zeolite type A is calculated to contain 10.0% by weight of ammonium ion (NH ₄ ⁺ ). The material prepared as described above had an ammonium ion content of 5.04% by weight, corresponding to 50.4% ion exchange.

Example 2

Production of MAP-type zeolite exchanged for ammonium ion

A zeolite MAP of the sodium type, prepared in a similar manner to that described in Example 1 of EP 384 070A, was converted to an ammonium ion-substituted zeolite MAP by the procedure of Example 1.

The fully ion-exchanged MAP zeolite is calculated to contain 10.4% by weight of ammonium ion. The ammonium ion content of the ion-exchanged material was 7.95% by weight, which corresponds to an ion exchange of 76.4%.

Example 3

Production of zeolite type A exchanged for lithium ion

The zeolite type 4A in sodium form was converted (partially) to the lithium ion-exchanged zeolite in a similar manner to that used in Example 1, using a 0.2 M solution of lithium chloride in place of the ammonium sulfate solution.

Example 4

Preparation of lithium ion-exchanged MAP type zeolite

The zeolite MAP type zeolite in lithium form was prepared from the zeolite MAP type zeolite used in Example 2 according to the procedure described in Example 3.

Example 5

Preparation of hydrogen ion-exchanged type A zeolite

150 g of hydrated sodium-containing zeolite type 4A were suspended in 3 l of deionized water. The pH of the slurry was monitored using a pH electrode. The pH was adjusted to 8.0 by slow addition of 0.1 M hydrochloric acid. After addition of the acid, the zeolite was filtered, washed with deionized water and dried in an oven at 100 ° C. The dried zeolite was ground in a mortar and then the whole of the bridg

HU217991 több was stored at ambient temperature for several days in order to facilitate the accumulation.

Example 6

Preparation of Hydrogen-ion-exchanged MAP-type zeolite A partially hydrogen-exchanged MAP-type zeolite was prepared from the MAP-type zeolite in sodium form used in Example 2 according to the procedure described in Example 5.

Comparative Example A)

Production of zeolite type A exchanged for potassium

Partially potassium ion-exchanged type A zeolite was prepared from sodium type A zeolite used in Example 1 using the procedure described in Example 3, except that the lithium chloride solution was replaced by a 0.2 molar potassium chloride solution.

Comparative Example B)

Preparation of Potassium-Exchanged MAP-Type Zeolite The partially potassium-ion-exchanged MAP-type zeolite was prepared from the MAP-type zeolite in sodium form used in Example 2 using the procedure described in Example 4, except that the lithium chloride solution was 0.2 mol / l. It was replaced by 1 potassium chloride solution.

7-10. examples

Preparation of Type 4A Zeolite Samples Partially Exchanged with Sodium / Ammonium Ion Zeolite in Hydrated Sodium Form

150 g samples were suspended in various concentrations of ammonium sulfate solution at pH 9 for 1 hour at 40 ° C. The zeolite was then filtered, washed and dried in an oven at 100 ° C. The dried zeolite was ground in a mortar and stored under ambient conditions for several days for complete hydration. The products obtained were analyzed to determine the actual rate of ion exchange to ammonium ion.

Pclda number ammonium sulphate concentration (mol / l) ammonium ion content (crowd%) The ion exchange degree (%) 7th 0.10 1.31 13 8th 0.21 2.35 23 9th 0.41 3.60 35 10th 0.82 4.74 46

11-13. examples

Preparation of MAP-type Zeolite Samples Partially Exchanged with Sodium / Ammonium Ion. Examples 4 to 5 were prepared using 4 MAP zeolite samples partially exchanged for sodium / ammonium ions. Details of the preparation and analytical assays are summarized below.

Example number ammonium sulphate concentration (mol / l) Ammóniumion- content (%, By weight) The degree of ioncscrc (%) 11th 0.11 1.13 11 12th 0.21 2.47 24 13th 0.42 5.89 57.5 14th 0.84 8.74 85

15-30. examples

Comparative Example C) -K)

Stability of sodium percarbonate

15-17. examples

Comparative Examples C) and D)

Stability of sodium percarbonate in zeolite / percarbonate type A mixtures

Test samples were prepared by:

3.75 g of the zeolite listed below are mixed with 1.25 g of sodium percarbonate (Oxyper, 500-710 µm screen fraction, manufactured by Interox) to give a mixture containing 75% by weight of zeolite and 25% by weight of percarbonate.

Example Type of zeolite C.) sodium zeolite type A (Wessalith P) 15th zeolite type A exchanged for ammonium ion (Example 1) 16th zeolite type A exchanged for lithium ion (Example 3) 17th zeolite type A exchanged for hydrogen ion (Example 5) D) zeolite type A exchanged for potassium ion [Comparative example A]

Storage stability was determined by the following accelerated storage test under extremely unfavorable conditions. The test is designed to detect differences in a shorter period of time than would be possible in a test using real-world and standard packaging.

Samples were stored in open glass bottles at 37 ° C and 70% relative humidity. At regular intervals, the powder mixture in the flasks was analyzed for residual active oxygen content. The following results were obtained during the tests.

Example Residual active oxygen 0 3 6 10 14 days later C.) 100 62.7 47.7 33.4 16.6 15th 100 92.3 86.4 78.0 68.6 16th 100 85.0 75.7 60.9 55.7

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Table (continued)

Example Residual active oxygen 0 3 6 10 14 days later 17th 100 85.0 67.0 50.0 36.6 D) 100 54.0 34.5 19.5 12.3

The results show that zeolites exchanged for ammonium, lithium and hydrogen ions significantly increase the storage stability of sodium percarbonate. Ammonium ion exchanged material shows the best result, while potassium ion exchanged material shows worse results than zeolite containing only sodium.

-20. examples

Comparative Examples E) and F)

Stability of sodium percarbonate in MAP zeolite / percarbonate mixtures Test samples are shown in Figs. was prepared as described in Example, each sample contained 3.75 g of a zeolite (75 parts by weight ⁰ /)) and sodium percarbonate (1.25 g, 25%) as follows.

Example Type of zeolite E) sodium zeolite containing MAP (starting material for Examples 2 and 4) 18th zeolite MAP of ammonium ion exchange (Example 2) 19th lithium ion-exchanged MAP type zeolite (Example 4) 20th zeolite MAP type exchanged for hydrogen ion (Example 6) F) zeolite MAP, exchanged for potassium ion [Comparative Example B]

Storage stability at 37 ° C and 70% relative humidity in open glass bottles is shown in FIGS. as described in Examples. The following results were obtained during the tests.

Example Residual active oxygen 0 3 6 10 14 days later E) 100 73.7 59.1 37.7 27.3 18th 100 94.3 91.4 90.2 90.9 19th 100 92.1 90.9 83.0 73.6 20th 100 93.4 84.0 73.3 62.1 F) 100 61.5 40.9 24.5 14.1

A comparison of these results is shown in Figures 15-17. The results of Examples 1 to 4 show that further improvements in stability can be achieved by the invention by replacing zeolite type A with zeolite MAP.

It should be noted that the MAP type zeolite containing ammonium ion (Example 18) did not cause a significant loss of percarbonate even after 14 days in very unfavorable conditions when stored in an open container.

Similar to type A zeolite, the potassium ion exchanged material showed worse performance than the zeolite in its sodium form.

21-24. examples

Comparative Example G

Stability of sodium percarbonate in mixtures with sodium / ammonium ion exchanged zeolite type A samples

15-17. Examples 7 to 10 were repeated. Examples include zeolites partially exchanged for sodium / ammonium ions. Comparative Example G was prepared as a starting zeolite type A in sodium-only form. The results of storage stability were as follows:

Example Residual active oxygen 0 3 6 10 days later G) 68.2 54.6 29.8 12.7 21 (seventh) 94.6 89.8 73.9 56.4 22nd (8th) 94.1 90.5 83.0 69.8 23rd (9th) 90.9 90.5 82.5 66.4 24 (10th) 97.3 93.6 87.0 74.5

It can be seen that only 11% ion exchange can achieve significant improvement (Example 21).

25-28. examples

Comparative Example H)

Stability of sodium percarbonate in mixtures with different MAP / zeolite ion-exchanged sodium / ammonium ions

21-24. Examples 11 to 14 were repeated. Examples include zeolites partially exchanged for sodium / ammonium ions. Comparative Example H was prepared as a starting MAP zeolite in sodium-only form. The results of storage stability were as follows.

Example Residual active oxygen 3 5 10 17 days later H) 74.6 61.4 38.4 26.8 25 (11th) 95.5 91.6 81.8 77.7 26 (12th) 93.2 91.6 88.6 80.9

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Table (continued)

Example Remaining active oxygen 3 5 10 17 days later 27 (13th) 96.8 90.2 82.3 73.6 28 (14th) 95.2 90.0 80.5 72.7

The results are similar to those obtained with partially deionized zeolite type A, where the greatest improvement is apparently achieved when the degree of exchange to ammonium ion is at least 23% (Examples 26-28).

Examples 29 and 30

Comparative Examples J) and K)

Stability of sodium percarbonate in detergent granules

Detergent granules were prepared in a laboratory-sized granulator by granulating zeolite with a nonionic surfactant, in each case using just enough nonionic surfactant for granulation. The nonionic surfactant used was commercially available as Synperonic A7, a C12-C15 primary alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of alcohol (manufactured by ICI).

The zeolites used were the ammonium ion-exchanged zeolites of Examples 1 and 2 and the corresponding sodium-containing zeolites (starting materials used in Examples 1 and 2). The composition of the granules was as follows.

Example Type of zeolite Ncionic surfactant (g / 200 g zeolite) J) Well A 61.5 29th NH ₄ A (Example 1) 64.8 K) Well MAP 75.3 30th NH ₄ MAP (Example 2) 82.0

The granulate was sieved and a fraction of 250-700 µm was used to determine the storage stability of percarbonate in the assay described below.

Each test sample was prepared by mixing (8.75 g) detergent granulate (1.25 g) with sodium percarbonate. The composition of the test samples was therefore as follows.

Example Composition (% by weight) Zeolite Ncmionic surfactant percarbonate J) 66.9 20.6 12.5 29th 66.1 21.4 12.5

Example Composition (% w / w) Zeolite Nonionic surfactant percarbonate K) 63.6 23.9 12.5 30th 62.1 25.4 12.5

As in the previous examples, the samples were stored in open glass bottles at 37 ° C and 70% relative humidity. During storage tests the following results were obtained:

Example Residual active oxygen 0 6 9 14 days later J) 100 30.2 20.5 4.1 29th 100 83.9 77.7 51.6 K) 100 50.0 42.0 10.5 30th 100 90.0 90.9 79.5

31-35. examples

Comparative Examples L) to Q)

Stability of bleach catalyst

Example 31

Comparative Example L)

Detergent base powders were prepared by mixing zeolite type A in sodium or ion exchanged form with a mixture of liquid surfactants in a laboratory-sized granulator, wherein the mixture of surfactants is coconut alcohol sulfate (CocoPAS), -7EO contained nonionic surfactant and water. The zeolites were the same as those used in the previous examples: the type A zeolite exchanged for ammonium ion was the zeolite of Example 1, while the zeolite in the sodium-containing form was the starting material of Example 1. The differences in formulation reflect the different carrier capacity of the two zeolites.

The base powders were mixed with manganese catalyst granules to form powders of the following formulation.

Example L) Example 31 Zeolite type A (Na) * 65.5 - Zeolite type A (NH ₄ ) * (Example 1) - 68.6 cocoPAS 7.5 6.7 Coco 7EO 7.5 6.7 Coco 3EO 9.6 8.5 Soap 2.9 2.6 Water 2.0 1.8

HU217991 Β

Table (continued)

Example L) Example 31 Total weight of basic powder 95.0 95.0 catalyst by 5.0 5.0 100.0 100.0

* based on hydrated material

The formulation of the catalyst granulate is as follows

volt: catalyst (Mn 1, 4,7-Me ₃ TACN) 1.8 Zeolite MAP 46.6 Soap / fatty acid * 20.5 citric acid 22.2 titanium dioxide 8.9

100.0 * 30% neutralized mixture of C 12 -C 12 saturated fatty acids (60 weight% C 12 fatty acid, 17 wt% fatty acid 16, 20 wt% 18 fatty acid, 3 wt% 10 and 14 fatty acid).

Samples of each powder were stored in open powder bottles at 37 ° C and 70% relative humidity. After a storage time of 28 days, the powder samples of Example 31 and Comparative Example L were visually compared by 8 evaluators to determine relative discoloration. The test results were as follows:

number of port preference for example 31: 8 number of port preference for comparative example L: 0.

The powder of Example 31 showed a slight discoloration, while the powder of Comparative Example L showed a significant colorlessness. On the arbitrary scale of 0 to 10, evaluators assigned the following scores to discoloration:

Sample 31 powder: 3,

Comparative powder L): 6.

Example 32

Comparative Example M)

Detergent base powders were prepared by mixing Μ AP type zeolite containing sodium or in ion-exchanged form in a laboratory-sized granulator with a mixture of liquid surfactants used in Example 31 and Comparative Example L). The MAP type zeolite exchanged for ammonium ion was the starting material of Example 2 and the MAP type zeolite in sodium form was the starting material of Example 2. Again, the differences in formulation reflect the different carriers of the two zeolites.

The base powders were mixed with manganese catalyst granules to form powders of the following formulation.

Example M) Example 32 Zeolite MAP (Na) * 58.9 - Zeolite MAP (NH ₄ ) * (Example 2) - 63.6

Example M) Example 32 cocoPAS 9.2 8.0 Coco 7EO 9.2 8.0 Coco 3EO 11.7 10.1 Soap 3.5 3.1 Water 2.5 2.2 Total weight of basic powder 95.0 95.0 catalyst by 5.0 5.0 100.0 100.0

* based on hydrated material

Storage tests and evaluation of discoloration were performed as described in Example 31 and Comparative Example L). The following results were obtained: Number of port 32 preference for Example 32: Number of port preference for Example M port 2: 2.

Comparative Example M (sodium-containing zeolite MAP) had a significantly less colorless powder than Comparative Example L (sodium-containing zeolite A), having a previous discoloration score of 2.

Example 33

Comparative Example N)

The procedure of Example 31 and Comparative Example L) was repeated using different catalyst granules of the following composition:

catalyst (Mn 1, 4.7 Me ₃ TACN) 2.0 cetocetyl stearate 31.0 silica * 26.4 sodium bicarbonate 39.6 titanium dioxide 1.0

100.0 * Gasil 200TP trade name (manufactured by Crosfield).

The product of Example 33 contained 95% by weight of the base powder of Example 31 (zeolite type A exchanged with ammonium ion), while the composition of Comparative Example N) contained 95% by weight of the base powder (sodium-containing type A zeolite). Each powder additionally contained 5% by weight of catalyst granules. Storage studies were performed as described in the previous examples. The evaluation led to the following results:

number of port preference for example 33: 8, number of port preference for example N): 0.

The discoloration scores were as follows:

powder of Example 33: 0,

Comparative Example N powder: 8.

Example 34

Comparative Example P)

The procedure of Example 33 and Comparative Example N) was repeated with ammonium ion exchanged MAP

EN 217 991 Β with zeolite MAP (Example 34) and sodium zeolite MAP (Comparative Example P).

The composition of Example 34 contained 95% by weight of the base powder of Example 32 (zeolite MAP-exchanged with ammonium ion), while the composition of Comparative Example P) contained 95% by weight of the base powder (sodium-type zeolite MAP) of . Each powder also contained 5% by weight of catalyst granules. Storage studies were performed as described in the previous examples. The evaluation led to the following results:

number of port preference for example 34: 7, number of port preference for comparative example P): 1.

The discoloration scores were as follows:

powder of Example 34: 0,

Comparative Example P powder: 3.

Example 35

Comparative Example Q)

This example describes an accelerated storage assay for detecting the effect of the zeolite type on the decomposition of the Mn 1,4,7-Me ₃ TACN manganese catalyst. In this assay, the non-granular catalyst was in direct contact with the zeolite base powder.

The crystalline catalyst (0.26 g) was granulated with (3 g) 7EO nonionic surfactant and (10 g) zeolite to prepare the following formulations.

Example Q 35th Catalyst 1.96 1.96 Zeolite type A (Na) * 75.42 - Zeolite type A (NH ₄ ) * (Example 1) - 75.42 7EO nonionic surfactant ** 22.62 22.62 100.0 100.0

* calculated with hydrated substances ** oxoalcohol 12-15, 7EO, Synpcronic A7 kcrcskekcdclmi (manufactured by ICI)

The granules were stored at 37 ° C and 70% relative humidity and inspected at regular intervals for color.

The granules of Comparative Example Q) showed significant discoloration after storage for one hour, while the granules of Example 35 did not show discoloration even after 7 days of storage.

Claims (8)

PATIENT INDIVIDUAL POINTS A granular detergent, bleach or cleaning composition comprising crystalline aluminosilicate containing a moisture-sensitive bleaching component and a replaceable cation, characterized in that at least 5% by weight of the aluminum silicate replaceable cations are ammonium and / or lithium. and / or contains hydrogen ions. Composition according to claim 1, characterized in that it comprises zeolite A of aluminum silicate having a replaceable cation of 10-50% by weight of ammonium and / or lithium and / or hydrogen ions. Composition according to claim 1, characterized in that it contains up to 1.33 zeolites of silicon: aluminum atomic ratio of aluminum silicate having a replaceable cation of 10-90% by weight of ammonium and / or lithium, and / or hydrogen ions. 4. Referring to 1-3. Composition according to any one of claims 1 to 3, characterized in that it contains inorganic perso as a moisture-sensitive bleaching component. 5. A composition according to claim 4, wherein the inorganic perso is sodium percarbonate. A composition according to claim 1 which is a) from 2 to 60% by weight of at least one organic detergent surfactant, b) 10-80% by weight of a replaceable cation-containing crystalline aluminosilicate detergent builder c) a bleaching system comprising from 5 to 40% by weight of a moisture-sensitive bleaching component; d) and optionally other ingredients in an amount of up to 100% by weight, characterized in that the component (b) comprises aluminum silicate with ammonium and / or lithium and / or hydrogen ions. 7. Type P, up to 1.33 silicon: aluminum atomic (MAP type) zeolite, containing interchangeable cations, characterized in that the exchangeable cations contain at least 5% by weight of ammonium and / or lithium and / or hydrogen ions. . 8. Zeolite P according to claim 7, characterized in that the exchangeable cations contain ammonium and / or lithium and / or hydrogen ions in an amount of 10 to 90% by weight of acene.