JPH04342798A - Detergent composition - Google Patents

Abstract

PURPOSE: To obtain a detergent composition suitable for fabric washing in a domestic or commercial washing machine which comprises a detergent builder system composed of a detergent-active compound, specified zeolite, and a polycarboxylate polymer.

CONSTITUTION: An intended composition comprising a detergent builder system containing (A) at least one detergent-active compound selected from anionic, nonionic, cationic, amphoteric, and zwitter ion detergent-active compounds and their combinations and (B) (i) the alkali metal aluminosilicate of P-type zeolite of Si/Al of 1.33 or less (most preferably 1.10 or less) and (ii) a polycarboxylate polymer in the form of an acid and/or a base in a weight ratio of 2:1-10:1.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION This invention relates to detergent compositions, particularly those containing detergent builder systems which are a combination of certain aluminosilicates and polycarboxylate polymers, in domestic or commercial washing machines. The present invention relates to a granular detergent composition suitable for washing textiles.

0002

BACKGROUND OF THE INVENTION Heavy duty detergent compositions for washing textiles are usually
It contains detergent builder substances, which reduce the concentration of water-hardening calcium ions in the washing liquor, thus providing a cleaning effect as good in hard water as in soft water.

Alkali metal aluminosilicate ion exchangers, particularly crystalline sodium aluminosilicate salt zeolite 4A, are currently known as replacements for inorganic phosphate esters traditionally used as detergent builder agents in textile detergents. . It is also known that zeolites exhibit some inadequacy in cleaning enhancement compared to phosphate esters, with supplemental enhancement power being generally desirable. Many non-phosphoric acid high demand powder detergents currently on the European market contain homopolymers or copolymers of acrylic acid suitable for this purpose.

Detergent compositions enriched with crystalline aluminosilicates (zeolites) and also containing polyacrylates or acrylic acid/maleic acid copolymers are available, for example EP 221
777A, EP 240 356A, EP 27
0 240A, EP 340013A, EP 3
58 473A, 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); EP
228 011A and EP 291 869A
(Henkel); and EP 229 671A
(Kao Publishing).

Water softening or detergent builder granules based on zeolites and polycarboxylate polymers are
184 794A, EP 243 908A
, and EP344 629A (Henkel); E
P 289 767A and EP 289 76
8A (Degussa); GB 1 568
420 and GB 2210 055A (Colga
DE 3 316 513A (Ben
and DE 3 707 80
6A (Dispo-Kommerz AG).

EP 384 070A (Unile
ver company) claims a new zeolite P (maximum aluminum zeolite P, or zeolite MAP) with a particularly low silicon to aluminum ratio of less than 1.33, preferably less than 1.15. This material has been shown to be a more efficient detergent builder than common zeolite 4A.

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

EP released on March 27, 1991
419 036A (Unilever), in detergent builder additives for use in Baukasten (building block) products with separately packed main detergent powders, contains at least 5
0% by weight (anhydrous basis) of a water-insoluble alkali metal aluminosilicate; (ii) 15% to 20% by weight of sodium carbonate;
and (iii) an additive consisting of 2% to 12% by weight organometallic sequestering agent builder, which may be a polycarboxylate polymer.

Such builder additives are expressly excluded from the present invention.

0010

SUMMARY OF THE INVENTION A first aspect of the invention provides a detergent composition suitable for washing textiles containing (i) anionic, nonionic, cationic, amphoteric and zwitterionic detergent active compounds. (ii) (a) Zeolite P (hereinafter referred to as Zeolite M) having a silicon to aluminum ratio not exceeding 1.33;
(referred to as AP); and (b) a polycarboxylate polymer in acid and/or salt form; Detergent composition suitable for washing textiles, characterized in that it consists of a detergent builder system, the ratio of which is preferably in the range from 2:1 to 10:1, more preferably from 4.5:1 to 9.5:1. provide something.

A second aspect of the 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. % by weight of a polycarboxylate polymer, (a) a zeolite MAP (as defined above), and (b) an acid and/or
or a polycarboxylate polymer in salt form, wherein the ratio of zeolite MAP (a) (anhydrous basis) to polycarboxylate polymer (b) is preferably from 2:1 to 10:1, more preferably 4.5. :1 to 9.5:1.

A third aspect of the invention is a method of washing textiles comprising contacting the textiles with an aqueous cleaning solution 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 invention provides a detergent composition comprising a polycarboxylate polymer in acid and/or salt form as a builder in a detergent builder composition or a zeolite MAP suitable for the washing of textiles. provide a use.

[0014]

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

Detergent Active Compounds The detergent compositions of the present invention contain one or more detergent active compounds selected from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtures thereof. Contains a compound (surfactant) as an essential component. Many suitable detergent-active compounds are available and can be found in the literature, e.g.
“S” by chwartz, Perry and Berch.
surface-Active Agents an
d Detergents, Volumes I and II.

Preferred detergent active compounds that 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 include alkylbenzene sulfonates, especially linear alkylbenzene sulfonates with an alkyl chain length of C8-C15; primary and secondary alkyl sulfates, especially primary alkyl sulfates with C12-C15; alkyl ether sulfates; olefin sulfonates; Examples include xylene sulfonate; dialkyl sulfosuccinate; and fatty acid ester sulfonate. Sodium salts are generally preferred.

Nonionic surfactants which can be used include primary and secondary alcohol ethoxylates, especially aliphatic C12-C1 ethoxylated with an average of 3 to 20 mol of ethylene oxide per mole of alcohol.
5 primary and secondary alcohols; and alkyl polyglycosides.

Preferred detergent active systems suitable for compositions intended for use in electric washing machines include anionic non-soap surfactants, or non-ionic surfactants, or a combination of both in any proportion necessary. It consists of adding soap according to the amount.

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

Detergent Builder System The detergent builder system of the present invention contains two essential components, 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, most preferably 1.10.
Defined as an alkali metal aluminosilicate of zeolite P type having the following:

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

The silicon to aluminum ratio is preferably within the range of 0.9 to 1.33, more preferably 0.
．． It is within the range of 9 to 1.2.

Particularly preferred are zeolites 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 as CaO per gram of anhydrous aluminosilicate.

Zeolite MAP like other zeolites
contains water of hydrate, but for the purposes of this invention the amounts and percentages of zeolite are expressed as anhydrous.

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

Preferred polycarboxylate polymers are:
Homopolymers and copolymers of acrylic acid and/or maleic acid in acid and/or salt form. Particularly preferred polymers are acrylic acid homopolymers and acrylic acid/maleic acid copolymers. EP 25 551B (BAS
The acrylic acid/maleic acid copolymers disclosed by F. Co., Ltd.) are particularly suitable for this purpose.

[0030] Examples of high-molecular polycarboxylates that can be preferably used alone or in combination in the composition of the present invention include the following: Type of polymer Product name
Publisher Average molecular weight polyacrylate Versicol*
Allied 3500
E5
Colloids Polyacrylate Versicol* Alli
ed 27000
E7
Colloids Polyacrylate
Versicol* Allied
70000
E9 Col
roids polyacrylate Narlex*
National 50
00LD
30 Adhesives Polyacrylate Narlex* N
ational 25000
LD34
Adhesives Polyacrylate
Acrysol* Rohm &
1000
LMW-10 Haas
Acrysol*
Rohm & 2000
LMW-20
Haas polyacrylate
Acrysol* Rohm &
4500
LMW-45 Haa
Company S polyacrylate Acrysol*
Rohm & 60000
A1-N
Haas Polyacrylate Sokalan* BASF
2500
PA-20 polyacrylate
Sokalan* BASF
15000
PA-40 polyacrylate S
okalan* BASF
70000
PA-70 polyacrylate Soka
lan* BASF 2
50000
PA-110 ethylene/EMA*
Monsanto Methyl Vinyl Maleate Gantrez*
GAF Corpo-ether/maleic acid AN 119 ration company acrylate/Sokalan*
BASF Malate
CP5, CP7 Acrylic acid D
KW* National Phosphinate
Adhesives acrylic acid
Belsperse* Cib
a-Geigy Phosphinate Note * is a trademark The weight ratio of aluminosilicate to polymer is preferably in the range of 2:1 to 10:1, more preferably 4.5:
The ratio is 1 to 9.5:1.

Preferred builder systems Detergent compositions of the present invention preferably contain from 10% to 45% by weight.
% by weight more preferably from 12% to 30% by weight of zeolite MAP and from 2% by weight to 10% by weight and more preferably from 2% to 6% by weight of polymer.

Bleaching System The detergent composition according to the invention may also suitably contain a bleaching system. This preferably consists of one or more peroxy bleach compounds, such as inorganic persalts or organic peroxy acids, which can be used with bleach precursors to improve the bleaching action at low temperatures.

The bleaching system preferably consists of a peroxy bleach compound, preferably an inorganic persalt, optionally a precursor.

Preferred inorganic persalts are sodium perborate monohydrate and trihydrate and sodium percarbonate.

Preferred bleach precursors are peracetic acid precursors, especially tetraacetylethylenediamine (TAED);
Perbenzoic acid precursors; and US 4 751 0
15 and US 4 818 426 (Lever
Brothers Company) discloses novel quaternary ammonium and phosphonium bleach activators, particularly cholyl p-sulfophenyl carbonate (
CSPC).

[0036] If desired, the bleach system can also contain bleach stabilizers (heavy metal sequestering agents).

Other Components The composition of the present invention may contain water-soluble silicates such as sodium silicate, if necessary. The amount of soluble silicate in the compositions of the invention is at a relatively low level, preferably 5
It should be at most 1% by weight, more preferably at most 1% by weight.

The compositions of the present invention may suitably contain alkali metal carbonates, providing alkalinity rather than detergent builders. 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-refouling agents, inorganic salts such as sodium sulfate, enzymes, foam control agents, softeners, pigments, and color specs. and fragrances. The ones listed here are not all-inclusive.

Preparation of Detergent Compositions The detergent compositions of the present invention can be prepared by any suitable method. Particulate detergent compositions, which are preferred embodiments of the present invention, are prepared by spray drying a slurry of compatible heat-insensitive ingredients followed by continued spraying or post-addition of ingredients that are not amenable to processing via the slurry. Prepare as appropriate.

[0041] Detergent formulators of ordinary skill in the art will have no trouble 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 advantageous to add a portion of the zeolite MAP to be added at the final stage.

The particulate detergent compositions of this invention can be prepared in any suitable bulk density. at least 400
Particularly good are compositions having a bulk density of g/l, more preferably at least 500 g/l.

Detergent Builder Compositions The detergent builder systems of the present invention can themselves be used for water softening, or can be added to laundry liquors to improve the performance of unfortified or fortified detergent compositions in hard water. It exists as a composition that can be added.

[0045] Such compositions can be used, for example, if the laundry conditions require additives (builders, bleach), the main detergent powder is supplied with only the required separately packed additives. EP 419 036A (Unilever) published on March 27th
can form the building or water softening component of Baukasten (building block) detergent compositions as claimed in .

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

Compositions of this type consist of two essential ingredients (
Although in principle it does not contain any components other than zeolite MAP and polymers, in practice it is desirable to include other components, for example sodium carbonate, and binders such as nonionic surfactants or cellulose derivatives. however,
As mentioned above, the builder additives of the particular composition claimed in EP 419 036A do not form part of the present invention and are not claimed.

Builder compositions of this type that have been discussed can also be used as raw materials or premixes in the production of more fully formulated detergent compositions. However, the present invention includes within its scope detergent compositions prepared by mixing two builder materials (zeolite MAP and polymer) separately and independently with other detergent ingredients.

Further, unless otherwise specified, the present invention will be specifically explained below using examples in which parts and percentages are expressed by weight, but the present invention is not limited to these examples.

[0050]

【Example】

Examples 1 to 3, Comparative Example A Four types of detergent compositions containing zeolite and polycarboxylate polymer were prepared with the following formulation (parts by weight):

Part Linear alkylbenzene sulfonate
6.80 Non-ionic surfactant (7EO)
3.10 Nonionic surfactant (3EO)
6.90 koku
Ken
1.73
Builder system: Zeolite MAP or 4A (anhydrous base)
See below Acrylic acid/maleic acid copolymer antifoam granules
1.20 sodium carbonate
9.60 Sodium silicate
0.55TAED granules

6.60 Sodium perborate 1
hydrate
16.25Dequest 2047
0.75
Enzyme (Savinase 6.0T)
1.10 Fluorescent agent

0.21 Sodium carboxymethylcellulose 0.83


55.62 The polymer contains acrylic acid in the form of its sodium salt/
Maleic acid copolymer, Sokalan(TM) CP5
ex BASF, Germany, Ludwigshaf
It is en.

Zeolite MAP is EP 384
Prepared on pilot scale by a method similar to that described in Examples 1 to 3 of 070A (Unilever). The silicon to aluminum ratio of this is 1
．． It is 10.

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

The builder systems for the four compositions are as follows:
A 1
2 3 Zeolite 4A (anhydrous)
27.30 - -
−Moisture
7.50 Zeolite MAP (Anhydrous)
- 27.30 25.00 2
2.00 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 effectiveness was measured in a Candy™ washing machine with only the main wash cycle at 40°C. Two different product doses and two different hardnesses of water were used to launder 3 kg of stained test fabrics as detailed below.

The results, expressed as the difference in reflectance at 460 nm (ΔR460), are as follows: test fabric (1) cotton fabric contaminated with oil, silica and ink (2) contaminated with Indian ink and olive oil. (3) Cotton fabric contaminated with Indian ink, olive oil, silica and casein (4) Polyester/cotton fabric contaminated with Indian ink, olive oil, silica and casein (i) Water hardness 15° (French hardness) ), product dosage 4.8g/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) Water hardness 25° (French hardness), product dosage 6.4 g/l test cloth
A 1
2
3(1) 22.9
24.3 24.3 21
．． 6(2) 11.8
14.5 15.3 1
0.8 (3) 27.7
28.5 28.4
27.9 (4) 25.3
26.0 25.8
24.7 Example 4, Comparative Example B Two detergent compositions containing zeolite and polycarboxylate polymer were prepared with the following formulations:


%

B 4 linear alkylbenzene sulfonate
6.70 6.70 Nonionic surfactant (7EO) 3
．． 07 3.07 Nonionic surfactant (
3EO) 6.2
3 6.23 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 Sodium carboxymethyl cellulose 0.56
0.56 fluorescent agent

0.22 0.22 Antifoam granules

1.20 1.20T
AED granules
7.35
7.35 Sodium perborate monohydrate
14.00 14
．． 00 enzyme (Savinase 6.0T)
1.10 1.10 Moisture
11.00
11.00
1
00.00 100.00 Zeolite MAP, zeolite 4A and copolymer are the same as those used in Examples 1-3. Zeolite to polymer (
The ratio of (anhydrous basis) is 9.33 in each case, and the sum of zeolite and polymer is 31.0 in each case.

[0055] Cleaning effectiveness was measured in a Miele™ washing machine at 40° C. main wash cycle. Two different product doses and two different hardnesses of water were used to launder 4 kg of stained test fabrics as detailed below.

The results, expressed as the difference in reflectance at 460 nm (ΔR460), are as follows: test fabrics (1), (3) same as those 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 dosage 3.4g/l test fabric
B4(1)
18.
11 24.48 (3)
31.95
36.05 (5)
21.96 26.3
8(ii) Water hardness 40° (French hardness), Ca:M
g 2:1, product dosage 5.6g/
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 alkylbenzene sulfonate
6.00 Nonionic surfactant (7E
O) 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 antifoam granules

1.20 sodium carbonate

14.00 Sodium silicate

0.55TAED granules

3.00 Sodium perborate trihydrate
20.00Deq
uest 2047
0.75 enzyme (Savinas
e 6.0T) 0
．． 40 fluorescent agent

0.21 sodium carboxymethyl cellulose
0.83 moisture and salt

The 10.00 zeolite MAP and copolymer are the same as those used in Examples 1-4.

The ratio of zeolite MAP to copolymer is 6.00, and the total of zeolite MAP and copolymer is 1.
It is 4.00.

[0058] This composition showed an excellent cleaning effect.

Claims (5)

[Claims] 1. A detergent composition suitable for washing textiles comprising: (i) one or more selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent active compounds and combinations thereof; (ii) a detergent active compound of (a)
Zeolite P (hereinafter referred to as Zeolite MAP) with a silicon to aluminum ratio not exceeding 1.33
, and (b) a detergent builder system consisting of polycarboxylate polymers in acid and/or salt form,
The detergent composition. 2. Detergent composition suitable for washing textiles according to claim 1, characterized in that the zeolite MAP has a silicon to aluminum ratio of 1.10 or less. 3. The weight ratio of zeolite MAP (a) (anhydride based) to polymer (b) is from 2:1 to 10:
1. Detergent composition suitable for washing textiles according to any of the preceding claims, characterized in that it is within the range of 1. 4. Detergent composition suitable for washing textiles according to any of the preceding claims, characterized in that the polycarboxylate polymer is a homopolymer or a copolymer of acrylic acid and/or maleic acid. thing. 5. A detergent builder composition comprising at least 50% by weight (anhydrous basis) of zeolite MAP;
(a) Zeolite MAP having a silicon to aluminum ratio not exceeding 1.33, except for compositions consisting of 15% 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.