JPH07100799B2 - Detergent composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions, and in particular household or commercial washing machines containing a detergent builder system which is a combination of certain aluminosilicate and polycarboxylate polymers. It relates to a granular detergent composition suitable for laundering textiles.

[0002]

BACKGROUND OF THE INVENTION Heavy-duty detergent compositions for washing laundry are usually
It contains a detergent builder substance to reduce the concentration of water-hardening calcium ions in the wash liquor, thus giving a good cleaning effect in hard water as well as in soft water.

Alkali metal aluminosilicate ion exchangers, especially crystalline sodium aluminosilicate zeolite 4A
Is currently known as an alternative to the inorganic phosphate esters traditionally used as detergent builder agents in textile detergents. It is also known that zeolites show some deficiency in cleaning enhancement as compared to phosphate esters, and that a complementary enhancing power is generally desirable. Homopolymers or copolymers of acrylic acid are included as suitable for this purpose in many non-phosphoric acid high demand powder detergents currently on the European market.

Detergent compositions which are augmented with crystalline aluminosilicates (zeolites) and which also contain polyacrylates or acrylic acid / maleic acid copolymers are described, for example, in EP 221.
777A, EP 240 356A, EP 270 2
40A, EP 340013A, EP 358 473
A, EP 367 339A, EP 390251A,
And EP 352 135A (Unilever);
EP 215A, EP 63 399A, EP 66
915A, EP 130 640A and EP 137.
669A (Procter &Gamble); E
P 228 011A and EP 291 869A (H
Enkel); and EP 229 671A (Kao).

Water softening or detergent builder granules based on zeolites and polycarboxylate polymers are described in EP
184 794A, EP 243 908A, and E
P344 629A (Henkel); EP 289
767A and EP 289 768A (Deguss
Company a); GB 1 568 420 and GB 2210.
055A (Colgate); DE 3 316
513A (Benckiser); and DE 37.
07 806A (Dispo-Kommerz AG
Company).

EP 384 070A (Unilev
r company) has a particularly low silicon to aluminum ratio,
Novel zeolite P having less than 1.33, preferably less than 1.15 (maximum aluminum zeolite P,
Or zeolite MAP). This material has been shown to be a more efficient detergent builder than general zeolite 4A.

The present invention is based on the finding that the novel combination of zeolite MAP and polycarboxylate polymer provides a particularly effective detergent builder system.

EP published on March 27, 1991
419 036A (Univer) is a detergent builder additive for use in Baukasten (building block) products with a separately packed primary detergent powder, (i) may be zeolite MAP, at least 5
0 wt% (anhydrous basis) water insoluble alkali metal aluminosilicate, (ii) 15 wt% to 20 wt% sodium carbonate,
And (iii) claims an additive consisting of 2 wt% to 12 wt% organo sequestrant builder, which may be a polycarboxylate polymer.

Such builder additives are expressly excluded from the present invention.

[0010]

A first aspect of the invention is a detergent composition suitable for laundering textiles, comprising: (i) anionic, nonionic, cationic, amphoteric and zwitterionic detergent active compounds. And one selected from the combination
One or more detergent active compounds, (ii) (a) Zeolite P (hereinafter Zeolite M) having a silicon to aluminum ratio not exceeding 1.33.
AP), and (b) a detergent builder system consisting of a polycarboxylate polymer in the acid and / or salt form, wherein the zeolite MAP (a) (anhydrous basis) to the polycarboxylate polymer (b) A detergent composition suitable for laundering fabrics, characterized in that it comprises a detergent builder system whose ratio is preferably in the range of 2: 1 to 10: 1, more preferably 4.5: 1 to 9.5: 1. Provide things.

A second aspect of the present invention is a detergent builder composition comprising at least 50% by weight (anhydrous basis) zeolite MAP, 15% to 20% by weight sodium carbonate, and 2% to 12% by weight. Excluding compositions consisting of polycarboxylate polymer by weight%, (a) zeolite MAP (as defined above), and (b) polycarboxylate polymer in acid and / or salt form, The ratio of zeolite MAP (a) (anhydrous basis) to rate polymer (b) is preferably in the range of 2: 1 to 10: 1, more preferably 4.5: 1 to 9.5: 1. A featured detergent builder composition is provided.

A third aspect of the present invention is a method of laundering a fabric comprising the step of contacting a fabric with an aqueous wash liquor comprising a detergent composition as defined above and / or a detergent builder composition as defined above. I will provide a.

A fourth aspect of the present invention is a detergent composition comprising a polycarboxylate polymer in acid and / or salt form as a builder in a detergent builder composition or zeolite MAP suitable for laundering textiles. Provide a use.

[0014]

Detergent Compositions The detergent compositions of the present invention include a detergent active compound and a detergent builder system as essential ingredients.

Detergent Active Compound The detergent composition of the present invention comprises one or more detergent actives selected from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtures thereof. It contains a compound (surfactant) as an essential component. Many suitable detergent active compounds are available and are available in the literature, eg S
"S by chwartz, Perry and Berch
urface-Active Agents and
Well described in Volumes I and II of Detergents ".

Preferred detergent-active compounds which can be used are soaps and synthetic non-soap anionic and nonionic compounds.

Anionic surfactants are well known to those skilled in the art. Examples are alkyl benzene sulphonates, especially linear alkyl benzene sulphonates having an alkyl chain length C8-C15; primary and secondary alkyl sulphates, especially C12-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyls. Xylene sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred.

Nonionic surfactants which can be used include primary and secondary alcohol ethoxylates, especially aliphatic C12-C15 primary and secondary ethoxylated with an average of 3 to 20 moles of ethylene oxide per mole of alcohol. Alcohol; and alkyl polyglycosides.

Preferred detergent active systems suitable for compositions intended for use in electric washing machines include anionic non-soap surfactants, or nonionic surfactants, or a combination of both in any proportion, necessary. Depending on the addition of soap.

The total amount of detergent-active compounds is from 5% by weight to 4
A range of 0% by weight is suitable.

Detergent Builder System The detergent builder system of the present invention contains two essential ingredients, a zeolite MAP and a polycarboxylate polymer.

Zeolite MAP has a silicon to aluminum ratio of 1.33 or less, preferably 1.20 or less, more preferably 1.15 or less, and most preferably 1.1.
It is defined as a zeolite P-type alkali metal aluminosilicate having 0 or less.

Zeolite MAP and its use in detergent compositions are described in EP 384 070A (Unileve).
r company).

The silicon to aluminum ratio is preferably in the range 0.9 to 1.33, more preferably 0.9 to 1.2.

Particularly preferred is a zeolite MAP having a silicon to aluminum ratio of 1.07 or less.

Zeolite MAP usually has a calcium binding capacity of at least 150 mg CaO / g anhydrous aluminosilicate.

Zeolite MAP as well as other zeolites
Contains hydrated water, but for the purposes of the present invention, the amounts and percentages of zeolites are expressed as anhydrides.

The second essential ingredient of the detergent builder system of the present invention is a polycarboxylate polymer. Here, the "polycarboxylate polymer" means a water-soluble polymer polycarboxylic acid, a water-soluble polymer polycarboxylic acid salt, or a mixture thereof.

The preferred polycarboxylate polymers are:
Homopolymers and copolymers of acrylic acid and / or maleic acid in the acid and / or salt form. Particularly preferred polymers are acrylic acid homopolymers and acrylic acid / maleic acid copolymers. EP 25 551B (BASF
The acrylic acid / maleic acid copolymers disclosed by K.K.) are particularly suitable for the purpose.

[0030] As polymeric polycarboxylates which can be suitably used singly or in combination in the compositions of the present invention include the following: the original average molecular weight polyacrylate sale type Product name originated polymer Versicol ^* Allied 3500 E5 Colloids, Inc. polyacrylate Versicol ^* Allied 27000 E7 Colloids, Inc. polyacrylate Versicol ^* Allied 70000 E9 Colloids, Inc. polyacrylate Narlex ^* National 5000 LD 30 Adhesives, Inc. polyacrylate Narlex ^* National 25000 LD 34 Adhesives, Inc. polyacrylate Acrysol ^* Rohm & 1000 LMW -10 Haas Polyacry Rate ^{Acrysol * Rohm & 2000 LMW-20} Haas Co. polyacrylate ^{Acrysol * Rohm & 4500 LMW-45} Haas Co. polyacrylate ^{Acrysol * Rohm & 60000 A1-N} Haas Co. polyacrylate Sokalan ^* BASF Corp. 2500 PA-20 polyacrylate Sokalan ^* BASF Company 15000 PA-40 polyacrylate Sokalan ^* BASF Company 70000 PA-70 polyacrylate Sokalan ^* BASF Company 250,000 PA-110 ethylene / EMA ^* Monsanto maleic acid methyl vinyl Gantrez ^* GAF Corpo-ether / maleic acid AN 119 / Sokalan ^* BASF Murray CP5, CP7 Acrylic acid DKW ^* National phosphinate Adhesives Acrylic acid Belsperse ^* Ciba-Geigy phosphinate Note * The weight ratio of aluminosilicate to polymer is preferably in the range of 2: 1 to 10: 1, and Preferably 4.5:
1 to 9.5: 1.

Preferred Builder Systems The detergent compositions of the present invention are preferably 10% to 45% by weight.
%, More preferably 12% to 30% by weight zeolite MAP, and 2% to 10% by weight more preferably 2% to 6% by weight polymer.

[0032] Bleaching system The detergent compositions according to the present invention may contain a suitable bleach system. It preferably consists of one or more peroxybreach compounds which can be used with bleach precursors to improve the bleaching action at low temperatures, for example inorganic persalts or organic peroxyacids.

The bleaching system preferably comprises a peroxybleach compound, preferably an inorganic persalt, optionally a precursor.

The preferred inorganic persalts are sodium perborate monohydrate and trihydrate, and sodium percarbonate.

The preferred bleach precursor is a peracetic acid precursor, especially tetraacetylethylenediamine (TAE).
D); Perbenzoic acid precursors; and US 4 7510.
15 and US 4 818 426 (Lever Br.
new quaternary ammonium and phosphonium bleach activators disclosed in Others Company, especially cholyl p-sulfophenyl carbonate (CSPC).
Company).

If desired, the bleaching system can also contain a bleaching stabilizer (heavy sequestering agent).

Other Components The composition of the present invention can optionally contain a water-soluble silicate such as sodium silicate. The amount of soluble silicate in the composition of the present invention is relatively low, preferably 5
It is to be less than 1% by weight, more preferably less than 1% by weight.

The composition of the present invention may suitably contain an alkali metal carbonate to provide alkalinity rather than a detergent builder. The amount of alkali metal carbonate, preferably sodium carbonate, is suitably in the range 2% to 20% by weight, preferably 5% to 15% by weight.

Other substances that can be contained in the detergent composition of the present invention include fluorescent agents, anti-redeposition agents, inorganic salts such as sodium sulfate, enzymes, foam control agents, softening agents, pigments, coloring specifications. And fragrances. Not all are listed here.

Preparation of Detergent Compositions The detergent compositions of the present invention can be prepared by any suitable method. A particulate detergent composition, which is a preferred embodiment of the present invention, comprises spray drying a slurry of compatible heat insensitive ingredients followed by continued spraying or post addition of ingredients not suitable for processing via the slurry. Prepare appropriately.

Detergent formulators in the art will have no difficulty in determining which ingredients should be included in the slurry.

Both the zeolite MAP and the polymeric builder component are suitable for inclusion in the slurry,
For processing reasons it is expedient to add some of the zeolite MAP to be added in the final stage.

The particulate detergent composition of the present invention can be prepared to any suitable bulk density. At least 400
Compositions having a bulk density of g / l, more preferably at least 500 g / l, are particularly good.

Detergent Builder Composition The detergent builder system of the present invention can be used by itself in a wash liquor to improve the performance of the detergent composition in softening water, or in unhardened or hardened hard water. Present as a composition that can be added.

Such compositions are provided, for example, if the washing conditions require additives (builders, bleaches), the main detergent powder is supplied with only the separately packaged additives required, 1991. It is possible to form the building or water-softening component of a Baukasten (building block) detergent composition as claimed in EP 419 036A (Unilever) published March 27, 2010.

A typical composition of this type is 50% by weight.
To 80 wt% zeolite MAP (anhydrous basis), and 2 wt% to 10 wt% polycarboxylate polymer.

Compositions of this type are in principle free of components other than the two essential components (zeolite MAP and polymer), but in practice other components such as sodium carbonate, and nonionic surfactants. Alternatively, it may be desirable to include a binder such as a cellulose derivative. However, as mentioned above, the builder additives of the particular composition claimed in EP 419 036A do not form part of or claim the present invention.

The builder compositions of this type considered can also be used as raw materials or premixes in the production of more well formulated detergent compositions. However, the present invention includes within its scope detergent compositions prepared by mixing two builder substances (zeolite MAP and polymer) separately and separately from other detergent ingredients.

Further, the present invention will be described in detail below with reference to examples in which parts and percentages are shown by weight unless otherwise specified, but the present invention is not limited to these examples.

[0050]

EXAMPLES Examples 1 to 3, Comparative Example A Four detergent compositions containing zeolite and a polycarboxylate polymer were prepared with the following formulation (parts by weight): part linear alkylbenzene sulfonate 6.80 non Ionic surface active agent (7EO) 3.10 Nonionic surface active agent (3EO) 6.90 Soap 1.73 Builder system: Zeolite MAP or 4A (anhydrous basis) See below Acrylic acid / maleic acid copolymer Defoamer Granules 1.20 Sodium carbonate 9.60 Sodium silicate 0.55 TAED Granules 6.60 Sodium perborate monohydrate 16.25 Dequest 2047 0.75 Enzyme (Savinase 6.0T) 1.10 Fluorescent agent 0.21 Sodium carboxymethylcellulose 0.83 55.62 polymers, in the form of sodium salt a Acrylic acid / maleic acid copolymer, Sokalan (TM) CP5 ex BA
SF company, Ludwigshafen, Germany.

Zeolite MAP is EP 384 07
Prepared on a pilot scale by a method similar to that described in Examples 1-3 of OA (Univer). The silicon to aluminum ratio of this is 1.1.
It is 0.

Zeolite 4A is a Wessalith
(Trademark) P powderex Degussa.

[0053] 4 builder system types of compositions are as follows: A 1 2 3 Zeolite 4A (anhydrous) 27.30 - - - Water content 7.50 Zeolite MAP (anhydrous) - 27.30 25. 00 22.00 Water 7.20 6.60 5.80 Polymer 4.50 4.50 4.50 4.50 Ratio (a) :( b) (6.07) 6.07 5.56 4. 89 Total (a) + (b): Part 31.80 31.80 29.50 26.50% 33.50 33.60 32.16 30.14 Cleaning effect is 40 ° C. in Candy ™ washing machine. Was measured only in the main washing cycle. 3 kg of stain test cloth as detailed below was washed using two different product doses and two different hardness waters.

The results, expressed as the difference in reflectance at ₄₆₀ nm (ΔR ₄₆₀ ), are as follows: test cloth (1) cotton cloth contaminated with oil, silica and ink (2) with Indian ink and olive oil Contaminated polyester / cotton cloth (3) Cotton cloth contaminated with Indian ink, olive oil, silica and casein (4) Polyester / cotton cloth contaminated with Indian ink, olive oil, silica and casein (i) Water hardness 15 ° (France Hardness), product dose 4.8 g / l Test cloth A 1 2 3 (1) 20.4 23.0 23.6 22.2 (2) 12.5 14.7 13.6 10.7 (3) 27.4 28.1 27.9 26.8 (4) 24.1 24.8 25.2 24.5 (ii) hardness 25 ° water (French hardness), the product dosage 6.4 g / Test cloth A 1 2 3 (1) 22.9 24.3 24.3 21.6 (2) 11.8 14.5 15.3 10.8 (3) 27.7 28.5 28.4 27. 9 (4) 25.3 26.0 25.8 24.7 example 4 was prepared by two of the following blending composition a detergent composition comprising a Comparative example B zeolite and polycarboxylate polymer:% B 4 Linear alkyl benzene sulfonate 6.70 6.70 Nonionic surfactant (7EO) 3.07 3.07 Nonionic surfactant (3EO) 6.23 6.23 Soap soap 1.83 1.83 Builder system: Zeolite MAP-28.00 Zeolite 4A 28.00-Acrylic acid / maleic acid copolymer 3.00 3.00 Sodium carbonate 15.08 15.08 Sodium silicate 0.46 0.46 Nato Umcarboxymethyl cellulose 0.56 0.56 Fluorescent agent 0.22 0.22 Defoamer granules 1.20 1.20 TAED granules 7.35 7.35 Sodium perborate monohydrate 14.00 14.00 Enzyme ( Savinase 6.0T) 1.10 1.10 Water content 11.00 11.00 100.00 100.00 Zeolite MAP, Zeolite 4A and copolymer are the same as those used in Examples 1 to 3. is there. The ratio of zeolite (anhydrous basis) to polymer is 9.33 in each case and the sum of zeolite and polymer is 31.0 in each case.

The cleaning effect was measured in a Miele ™ washing machine with a main wash cycle of 40 ° C. 4 kg of stain test cloth as detailed below was washed using two different product doses and two different hardness waters.

The results, expressed as the difference in reflectance at ₄₆₀ nm (ΔR ₄₆₀ ), are as follows: Test cloths (1), (3) Same as in Examples 1 to 3 (5) Cotton cloth contaminated with Indian ink, olive oil, silica and a small amount of casein (i) Water hardness 20 ° (French hardness), Ca: Mg 2: 0, product dose 3.4 g / l Test cloth B 4 (1 ) 18.11 24.48 (3) 31.95 36.05 (5) 21.96 26.38 (ii) Water hardness 40 ° (French hardness), Ca: Mg 2: 1, product dose 5. 6 g / l test cloth B 4 (1) 14.32 21.07 (3) 27.45 31.01 (5) 18.77 21.29 Example 5 Low percentage of zeolite MAP and acrylic acid /
A composition containing a maleic acid copolymer was prepared as follows: Linear alkyl benzene sulfonate 6.00 Nonionic surfactant (7EO) 2.75 Nonionic surfactant (3EO) 4.25 Soap 1.75 Zeolite MAP (anhydrous base) (a) 12.00 Acrylic acid / maleic acid copolymer (b) 2.00 Defoamer granules 1.20 Sodium carbonate 14.00 Sodium silicate 0.55 TAED granules 3.00 Perborate Sodium trihydrate 20.00 Dequest 2047 0.75 Enzyme (Savinase 6.0T) 0.40 Fluorescent agent 0.21 Sodium carboxymethyl cellulose 0.83 Moisture and salt 10.00 Zeolite MAP and copolymer are examples. It is the same as that used in 1 to 4.

The ratio of zeolite MAP to copolymer is 6.00 and the sum of zeolite MAP and copolymer is 14.00.

This composition showed a good cleaning effect.

Claims (5)

[Claims] 1. A detergent composition suitable for laundering textiles, comprising one or more selected from (i) anionic, nonionic, cationic, amphoteric and zwitterionic detergent active compounds and combinations thereof. (Ii) (a) Zeolite P (hereinafter Zeolite M) having a silicon to aluminum ratio not exceeding 1.33.
And AP)), and (b) a detergent builder system consisting of a polycarboxylate polymer in the acid and / or salt form.
The detergent composition. 2. A detergent composition suitable for laundering textiles according to claim 1, characterized in that the zeolite MAP has a silicon to aluminum ratio of 1.10 or less. 3. A weight ratio of zeolite MAP (a) (anhydrous basis) to polymer (b) is from 2: 1 to 10 :.
A detergent composition suitable for laundering textiles according to any of the preceding claims, characterized in that it is in the range 1. 4. Detergent composition suitable for washing textiles according to any of the preceding claims, characterized in that the polycarboxylate polymer is a homo- or copolymer of acrylic acid and / or maleic acid. Stuff. 5. A detergent builder composition comprising at least 50% by weight (anhydrous basis) of zeolite MAP, 1.
(A) Zeolite MAP having a silicon to aluminum ratio not exceeding 1.33, excluding compositions comprising 5% to 20% by weight sodium carbonate and 2% to 12% by weight polycarboxylate polymer, And (b) a polycarboxylate polymer in acid and / or salt form.