JPH01146997A - Phosphorus free washing bleaching agent composition - Google Patents

Abstract

PURPOSE: To provide the subject composition having excellent cleaning and stain-removel performance, by blending a detergent-active material with a water- insoluble aluminosilicate cation-exchange material, citric acid or an alkali metal citrate, and an inorganic peroxide compound, a peroxybenzoic acid bleach precursor.

CONSTITUTION: This non-phosphorus detergent bleach composition of a solution pH 8-11 (at a conc. of 2-10 g/l) is obtained by blending at least one kind of the detergent-active material such as organic soap and synthetic detergent surfactant by 5-40 wt.% with water-insoluble aluminosilicate cathion-exchange material of a grain size of 0.1-10 μ such as zeolite A of formula I (x is 20-30) by 15-40 wt.%, citric acid or an alkali metal citrate by 1-15 wt.%, an inorganic peroxide compound such as perborate, percarbonate, and persilicate of an alikali metal by 5-35 pts.wt., a peroxyezoic acid bleach precursor such as sodium p- benzoiloxybenzene sulfonate in formula II by 1-10 wt.%, foam increasing agent such as an alkanolamide if necessary, and polycarboxylate polymer, etc.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a phosphorus-free cleaning bleach composition. The present invention particularly relates to laundry detergents containing aluminosilicate builders that have superior cleaning and stain removal efficacy over conventional ones.

The role and value of the phosphate detergent virgoo in laundry detergent compositions is well known. However, recently, there is a suspicion that soluble phosphates promote eutrophication of water in rivers, lakes, etc., so the use of phosphates such as alkali metal triphosphates is being reconsidered. It has become. Already, phosphate legislation in many countries has forced detergent manufacturers to significantly reduce phosphate levels in detergent compositions to near zero. Therefore,
There is an urgent need to develop built laundry detergent compositions that have zero or reduced phosphate content, yet are comparable to traditional triphosphate builder compositions in terms of overall detergent efficacy. It has become.

Additionally, as there is a current trend toward lower washing temperatures for fabrics, there is a need to improve the composition of detergent compositions so that they are effective even at low temperatures, such as 40° C. or lower.

Water-insoluble aluminosilicates, commonly known as zeolites, have been used as important substitutes for phosphates in detergent compositions, e.g. CB-8-142914.
3; GB-8-1470250, CB-Δ-15042
11, GI3-8-1529454 and US-^-40
64062). However, as a result of the bleach test,
The bleaching effectiveness of the aluminosilicate-built compositions was found to be lower than that of the phosphate-built products.

EP-El-0001853 contains 0.01 to 4% by weight of polyphosphate as a sequestering agent, and
Aluminosilicate builder detergent compositions containing 5 to 25% by weight of citric acid or citrate as a pl+ regulator are disclosed. This prior art composition contains 40
It is not very effective when used when washing at low temperatures below °C.

It is an object of the present invention to provide improved detergent compositions containing aluminosilicate builders that exhibit reliable cleaning and stain removal efficacy at low temperatures below 40°C.

It has been found that the above object can be achieved by incorporating an inorganic peroxide compound and a peroxybenzoic acid bleach precursor together with citric acid or an alkali metal citrate as the main bleach system.

Accordingly, the present invention provides at least one cleaning agent (a) from about 15% to about 40% by weight of a water-insoluble aluminosilicate cation exchange material; (b) from about 1% to about 15% by weight citric acid or alkali metal citrate; (c) from about 5% to about 35% by weight of an inorganic peroxide compound; and (d) from about 1% to about 10% by weight peroxyammonium, 9 ,
A phosphorus-free cleaning bleaching composition comprising a aromatic acid bleaching agent precursor.

The detergent compositions of the present invention necessarily include peroxybenzoic acid bleach precursors as bleach activators. This substance generates peroxybenzoic acid as a result of perhydrolysis. Other bleach precursors, such as the most commonly used tetraacetylene diamine (TAED), which generates peracetic acid, are much less effective and are therefore not suitable for use in the present invention.

The peroxybenzoic acid precursor is, for example, GB-Am8369.
88 known to those skilled in the art. Examples of precursors of this type include: phenylbenzoate; phenyl p-nitrobenzoate; 0-nitrophenylbenzoate;
Carboxyphenyl benzoate; p-bromophenyl benzoate; sodium or potassium benzoyloxybenzenesulfonate; and ammonium, dizoic anhydride.

The compound has the following general formula: %Formula% where R is H or a substituent selected from -N02 and halogen, and L is a leaving group (leav
ing group) whose conjugate acid is about 6 to about 1
It has a pKa of 3.

L can be essentially any suitable leaving group released from the bleach precursor as a result of the nucleophilic action of the perhydroxy anion HOO- on said bleach precursor. This complete hydrolysis reaction generates peroxybenzoic acid. Generally, for a group to be a suitable leaving group, it must exhibit an electron-withdrawing effect that facilitates nucleophilic action by the perhydroxy anion; , whose conjugate acid has a pKa of from 6 to 13, preferably from about 7 to about 11, most preferably from 8 to 11.

Specific examples of suitable compounds include those represented by the following formula: In the above formula, R1 is an alkylene group having 1 to 8 carbon atoms;
R2 is H or an alkyl chain having 1 to 8 carbon atoms, R' is phenyl or an alkyl chain having 5 to 18 carbon atoms,
Y is preferably -So, -M'', -COO-M' or -
Solubilizing group selected from 3O,M''
iziBBup).

A preferred peroxybenzoic acid bleach precursor is sodium p-benzoyloxybenzenesulfonate having the formula:

The inorganic peroxide compounds that can be used in the present invention can be true persalts or perhydrates that liberate hydrogen peroxide in aqueous solution.

Specific examples of the inorganic peroxide compounds include alkali metal perborates, percarbonates, and persilicates.

Perborate salts, particularly sodium perborate tetrahydrate or monohydrate, are particularly preferred as they are commercially available.

The inorganic peroxide compound and peroxybenzoic acid bleach precursor contained in the composition of the present invention in the above weight percent range are 0.
They may be present in a molar ratio of 5:1 to about 20:1, preferably 1:1 to 10:1. Depending on the washing conditions, a molar ratio of approximately 2=1 may be advantageous.

The compositions of the invention contain at least one cleaning agent, which may be an organic soap or a synthetic detergent surfactant. It typically contains about 5% to 40% by weight of an organic, anionic, nonionic, amphoteric or zwitterionic detergent compound, soap, or mixture thereof. Many suitable detersive compounds are commercially available and are described, for example, in US-4222905, U.S. Pat.
S-^-4239659, and 5cbu+artz,
“5surface Ac” by Perry and Berch
1ve eight Bents and Detergents”
, Vol. I and II.

Preferred detersive compounds that can be used are synthetic anionic compounds, soaps and nonionic compounds.

The synthetic anionic compound usually has 8 to 2 carbon atoms.
It is a water-soluble alkali metal salt of an organic sulfate or sulfonate having two alkyl groups.

Note that the term alkyl includes the alkyl portion of a higher aryl group. Examples of suitable synthetic anionic detergent compounds include sodium alkyl sulfates and potassium alkyl sulfates, especially those obtained by sulfating higher (CS-C98) alcohols made, for example, from tallow or coconut oil; 1,~C2o) sodium benzenesulfonate and potassium alkyl (09~C2o) benzenesulfonate, especially linear secondary alkyl (Coo~
C15) Sodium benzenesulfonate; sodium alkyl glyceryl ether sulfate, especially esters of higher alcohols derived from tallow or coconut oil and esters of synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulfonate and sodium monoglyceride sulfonate of said fatty acids; (aS-C1ll) Sourium and potassium salts of sulfuric acid esters of reaction products of aliphatic alcohols with alkylene oxides, especially ethylene oxide; salts of fatty acids such as coconut oil fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Reaction products: sodium and potassium salts of fatty acid amides of methylcurin; monosulfate alkanes, such as those derived by reacting α-olefins (08-C2o) with sulfur lithium bisulfite, and random sulfonates. Those derived by reacting paraffins with SO□ and C12 to form them followed by hydrolysis with base; and sulfonic acid olefins. The term sulfonic acid olefin refers to olefins, especially et al.
Refers to a substance formed by reacting an a-C20 α-olefin with 303, neutralizing and hydrolyzing the resulting reaction product. Suitable soaps are long chain C8~C2□
Alkali metal salts of fatty acids, such as sodium soaps of tallow, coconut oil, palm kernel oil, palm oil or hydrogenated rapeseed oil fatty acids or mixtures thereof. Preferred anionic detergent compounds are (-1 to C15) sodium alkylbenzene sulfonates and (C,6 to C,,) sodium alkyl sulfates.

Examples of suitable non-ionic detergent compounds that may be used include the reaction products of alkylene oxides, usually ethylene oxide, and alkyl (CS-C2)phenols, usually of 5 to 25 EO, i.e., 5 to 25 EO per molecular groove. Containing ~25 units of ethylene oxide; aliphatic (C, ~Cu
e) condensation products of primary or secondary linear or branched alcohols with ethylene oxide, usually from 6 to 30E
as well as reaction products obtained by condensation of ethylene oxide and propylene oxide/ethylenediamine reaction products. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary posphine oxides and dialkyl sulfoxides.

The detergent composition of the present invention may contain mixtures of detersive compounds, such as a mixture of a plurality of anionic compounds or a mixture of anionic and nonionic compounds. In particular, mixtures of anionic compounds and non-ionic compounds exhibit the property of controlling and suppressing foaming. Compositions for use in automatic washing machines that are sensitive to foaming have such properties. It is advantageous to have one.

Although appropriate amounts of amphoteric or zwitterionic cleansing compounds may be used in the compositions of the present invention, it is generally preferable not to use such compounds since they are relatively expensive. Even when amphoteric or zwitterionic detersive compounds are used, they are usually applied in small amounts in compositions based on more common synthetic anionic and/or nonionic detergent compounds.

The detergent compositions of the present invention also contain from 15% to about 40% by weight, preferably 2% by weight, of a water-insoluble aluminosilicate cation exchanger.
It may contain from 0% to 35% by weight.

This aluminosilicate may be crystalline or amorphous;
As a preferable specific example, the following formula ■Mz[(8102>
Examples include those represented by Z (SiO2)y]xl120 1.

In the above formula, M represents a calcium exchange cation, Z and y are 6 or more, and the molar ratio of zNy is about 1.0 to about 0.
5, and X is 5 or more, preferably about 7.5 to about 276
, more preferably about 10 to about 264. The aluminosilicate material has a hydrated form, preferably crystalline and about 10% to about 28%, more preferably about 18%
Contains ~22% water.

The aluminosilicate ion exchange material further has a particle size of about 0.1 microns to about 10 microns, preferably about 0.2 microns.
Micron - also has the characteristic of being approximately 4 microns. By "particle size" herein is meant the average diameter of the particles of a given ion exchange material as determined by conventional analytical methods such as microscopic measurements using, for example, a scanning electron microscope. The aluminosilicate ion exchange material used in the present invention also has a calcium ion exchange capacity of 200 mg equivalent or more per gram of aluminosilicate, calculated on an anhydrous basis.
Corresponds to the hardness of water equivalent to aCO3, usually about 300
It also has the characteristics of +n g/ffl/g to about 352 m8/ji/g. The aluminosilicate ion exchange materials of the present invention further have a calcium ion exchange rate of at least about 2 grains Ca++/gallon/minute (on an anhydrous basis) per gallon of aluminosilicate, and typically about 2 grains/gallon/minute. /g/gal ~ about 6 grains/gal/
min/g/gal. These values are based on calcium ion hardness. Aluminosilicates suitable for use as builders exhibit a calcium ion exchange rate of at least about 4 grains/gal/min/g/gal.

Aluminosilicate ion exchange materials useful in practicing the present invention are commercially available and can be naturally occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is described, for example, in US-8-
3985669.

Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are those commercially available under the names Zeolite^, Zeolite I-8, Zeolite I-X, Zeolite IIs, and mixtures thereof.

In a particularly preferred embodiment, the crystalline aluminosilicate, the ion exchange material is a zeolite, and the formula: In particular, it is about 27.

Zeolite 1-
8102)6 (Sin□)6] 7.5820 zeolite 1-HS<,,a is a suitable material.

The detergent compositions of the present invention further contain an alkali metal citrate or citric acid, from about 1% to about 15% by weight of the composition.
Preferably it contains 2 to 10% by weight. A preferred alkali metal citrate is sodium citrate, especially trisodium citrate or C6H5O, , Na, , 21120.

In addition to the above-mentioned ingredients, the detergent composition of the present invention contains conventional additives that are generally available on the market. For 1 ■ For 1 product
may be included in the amount to be used. Examples of such additives include foam enhancers such as alkanolamides, especially monoethanolamides derived from palm kernel oil and coconut fatty acids; foam suppressors such as alkyl phosphates, silicones and waxes. : Storium carboxymethyl cellulose (
SCMC), polyvinylpyrrolidone (PVP) and anti-resettling agents such as cellulose ethers such as methylcellulose, ethylhydroxyethylcellulose.

Stabilizers such as ethylenediaminetetraacetate-1;
fabric softeners; inorganic salts such as sodium sulfate and sodium carbonate; and fluorescent agents, fragrances, enzymes such as proteolytic, amylolytic and lipolytic enzymes, which are usually present in very small amounts; bactericides and colorants. Can be mentioned.

Although not an essential component, polycarboxylate polymers may also be used if desired, for example in an amount of about 0.5-6% by weight of the total composition. The polycarboxylate polymer used in the present invention has maleic acid as the first monomer,
- derived from laconic acid, itaconic acid or mesaconic acid and unsaturated polycarboxylic acids such as ethylene, methyl vinyl ether, acrylic acid or methacrylic acid as second monomer, at least about 10 mol%, preferably at least about 20 mol% copolymerized polycarboxylic acids and salts thereof containing polycarboxylic acid units and having a weight average molecular weight of at least about 1,000,000, preferably at least about 30,000; Preferably about 5000 to about 50,000
0 homopolyacrylates and homopolymethacrylates; and mixtures thereof.

The cleaning bleaching composition of the present invention is alkaline, advantageously having a solution pH (2 to Log, #) of 8 to 11.

The optimum pH is 8-9. For example, a wash pl+ of 8.5 appears to provide the most balanced conditions for adequate bleaching, cleaning and enzymatic stain removal.

The detergent compositions of the present invention, which may require additives such as borax to adjust the It can be manufactured by any of the known techniques most commonly used in the manufacture of laundry compositions. Preferably, however, an aqueous slurry containing one or more surfactants, an aluminosilicate, and an alkali metal citrate is spray-dried to form a detergent base powder, and a peroxybenzoic acid bleach precursor is added to the base powder. The heat-sensitive components are prepared by adding heat-sensitive components including peroxides, inorganic percompounds, enzymes, and any other components as desired. Alternatively, the alkali metal citrate may be dried separately and then mixed with the spray-dried base powder. Preferably, the bleach precursor and enzyme are added in granular form. The method used to prepare the compositions of the present invention provides a moisture content of less than or equal to about 15% by weight, preferably from about 7% to about 14% by weight.・It is preferable to select j1 in such a way that a product having the following properties can be obtained.

Hereinafter, the present invention will be explained in more detail by giving non-limiting examples.
Explain.

] - Aqueous detergent slurry was spray-dried to form a detergent basic powder composition (8), and this composition was blended with the granular composition (B) to produce a granular phosphorus-free detergent composition. .

Sodium 1-Rium 9.0 Aliphatic alcohol-7 Ethoxylate 1-1,5 (zeolite 8) 24.0
Sodium sulfate (anhydrous) 0.3 Sodium carboxymethyl cellulose 0.5 Sodium ethylenediaminede I-raacetate-1~ (EDT^) 0.2 I-lium carbonate (Na2COz) 2.0 Water and fluorescent agent (0,13 ) 7.6 Group J Shijutsu Kogen - Sodium perborate hydrate 13, 0 anti-foaming agent
25 acid 1-lium
5.0 Sothorium sulfate
29.9 The above formulations without the addition of trisium citrate, as well as trisodium citrate at levels of 0%, 1%, 2%, 3%, 5%, 10% by weight. The blended composition added to p
8g/in water at 40°C, 24°FH buffered to l+8.5
Tergotometer (Tergoto
A washing test was conducted by washing for 30 minutes with +neLer).

The bleaching effect on black tea and red wine stains was determined.

The results are shown in Table I.

Table 1 Composition 1 Nakohachi/B+ 0% citrate 6.4 2
0.1 to composition/B+ 1% citrate 8.2
26.3 To composition/B+2% citrate 9.6
29.9 Composition^/B←3% citrate 11.7
32.0 Composition^/B+5% Citrate 13.
2 33.9 Composition^/B+10% citrate
14.4 35.7 Jitsufu Kuchijiru U- A similar comparative test l~ was conducted regarding black tea and red wine stains, detergency, and protein stain removal effects (enzyme action). The results are shown in Table 2.

Table 2 □ 0°≦ Citrate 8.1 24.5 25.6
34.2 years old Adult/B + 5% citrate 13.8 32.6 26.3
34.8 These results show that tris-I-lium citrate increases the bleaching effect on tea and wine stains without compromising the detergency and enzymatic activity, ie the protein stain removal effect.

Claims (6)

[Claims] (1) at least one cleansing agent; and (a) about 1
from about 5% to about 40% by weight of a water-insoluble aluminosilicate cation exchange material; (b) from about 1% to about 15% by weight of citric acid or alkali metal citrate; (c) from about 5% to about A phosphorus-free cleaning bleach composition comprising 35% by weight of an inorganic peroxide compound, and (d) about 1% to 10% by weight of a peroxybenzoic acid bleach precursor. (2) - 5 to 40% by weight of said detersive agent selected from anionic, nonionic, amphoteric, zwitterionic detergent compounds, soaps and mixtures thereof; - said aluminosilicate cation exchanger; 2. Composition according to claim 1, characterized in that it comprises from 20 to 35% by weight of the substance; and from 2 to 10% by weight of said citric acid or alkali metal citrate. (3) The composition according to claim 1 or 2, wherein the peroxybenzoic acid precursor is sodium p-benzoyloxybenzenesulfonate represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ . (4) The composition according to any one of claims 1 to 3, wherein the alkali metal citrate is trisodium citrate. (5) A composition according to any one of claims 1 to 4, characterized in that the solution pH (at 2 to 10 g/l) is 8 to 11. (6) The composition according to claim 5, wherein the solution pH is 8 to 9.