KR920002085B1 - Non-phosphorus detergent bleach compositions - Google Patents

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Description

Murine bleach composition

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleach-free bleach composition, and more particularly to a laundry detergent bleach composition constructed of aluminosilicate with improved cleaning and degreasing effects. The role and value of phosphate detergency aids in laundry detergent compositions is well known. Recently, however, the use of phosphate supplements, such as alkali metal salts of triphosphates, needs to be reviewed, as water-soluble phosphates have been negotiated to accelerate eutrophication of aquatic plants. Already in many countries the law requires detergent manufacturers to produce detergent compositions by drastically reducing the phosphate content in detergent compositions to nearly zero. Therefore, there is a need for a laundry detergent composition that is comparable to conventional triphosphate compositions in terms of overall cleaning effect with little or no phosphate.

There is also a need to improve the composition of the detergent composition to effectively wash at low washing temperatures, for example below 40 ° C., in keeping with the current trend of preferring low fabric washing temperatures. Water-insoluble aluminosilicates, widely known as zeolites, are used in detergent compositions as phosphate replacement aids (eg GB-A-1429143, GB-A-1470250, GB-A-1504211, GB-A-1529454, and US). See A-406062)

However, the bleaching experiment demonstrated that the bleaching effect of the aluminosilicate build composition was much lower than that of the phosphate build composition. EP-B-0001853 discloses aluminosilicate build detergent compositions containing 0.01-4% by weight of polyphosphonates as metal sequestrants and 5-25% by weight of citric acid or strate as pH adjusting agents. However, the composition is not satisfactory when used to wash in a low washing temperature range of 40 ° C. or lower.

It is an object of the present invention to provide an improved aluminosilicate build detergent composition having practically effective detergency and degreaser capability at low washing temperatures below 40 ° C.

This object can be achieved by incorporating an inorganic peroxide and a peroxybenzoic acid bleaching precursor material as the main bleaching system together with citric acid or an alkali metal salt of citric acid.

According to the present invention one or more detergent active materials and (a) about 15-40% by weight of water-insoluble aluminosilicate cation-exchange material (b) about 1-15% by weight of citric acid or an alkali metal salt of citric acid (c) inorganic peroxide Provided is a rinse-free bleach composition containing about 5-35% by weight (d) about 1-10% by weight peroxybenzoic acid table precursor.

The detergent composition of the present invention essentially contains a peroxybenzoic acid bleaching precursor that generates peroxybenzoic acid upon perhydrolysis as a bleaching activator. Other bleaching precursors, such as the most widely used tetraacetylenediamine (TAED), which produce peracetic acid are not effective and are therefore not suitable for use in the present invention.

Peroxybenzoic acid precursors are published in scientific publications, for example GB-A-B36988. Examples thereof include phenylbenzoate, phenyl P-nitrobenzoate, O-nitrophenyl benzoate, O-carboxyphenyl benzoate, P-bromophenyl benzoate, benzoic oxybenzenesulfonate sodium or potassium, and benzoic anhydride There is this.

Such compounds have the general formula

Wherein R is or a substituent selected from -NO ₂ and halogen and L is a leaving group, the pKa of the diacid is in the range of about 6-13.

In essence L is suitable if the group is released from the bleaching precursor as a result of the nucleophilic attack on the peroxide anion, ie the bleaching precursor by HOO ⁻ . As a result of this perhydrolysis reaction, peroxybenzoic acid is produced. Generally, in order to be suitable as a leaving group, the electron attracting effect which promotes nucleophilic attack by a peroxide anion is preferably 8-11. Examples of suitable L are as follows.

Wherein R ¹ is C ₁ -C ₈ alkylene chain, R ² is H or C ₁ -C ₈ alkyl chain and R ³ is phenyl or C ₅ -C ₁₈ alkyl chain. Y is preferably selected from SO ₃ ^- M ⁺ , -COO ^- M ⁺ or -SO ₄ ^- M ⁺ as a soluble group.

Preferred peroxybenzoic acid bleaching precursor is sodium P-benzoyloxybenzene sulfonate having the following structure.

The inorganic peroxide used in the present invention is a peracid or perhydrate that generates hydrogen peroxide in aqueous solution. Examples of inorganic peroxides are alkali metal salts of perboric acid, percarbonate and persilicate, with double perborates, in particular sodium perborate tetrahydrate and monohydrate, for ease of purchase.

The weight percent of inorganic peroxide and peroxybenzoic acid bleaching precursor in the composition of the present invention described above should be determined such that its molar ratio is present within 0.5: 1 to about 20: 1, preferably 1: 1: 1-10: 1. do. Under certain washing conditions a molar ratio of about 2: 1 is preferred.

The composition of the present invention contains at least one detergent active material such as an organic soap or a detergent detergent.

Generally, about 5-40% by weight of organic, anionic, nonionic, amphoteric or zwitterionic detergent compounds, soaps or mixtures thereof are included. Various suitable detergent active materials are available, for example US-A-4222905 and-4239659 and Surface Active Agents and Detergents Vol. I and II. Schwartz, perry and berch).

Preferred detergent active compounds are synthetic anionic, soap and nonionic compounds. Synthetic anionic active compounds are generally water soluble alkali metal salts of organosulfuric acid and sulfonic acid having about C ₆ -C ₂₂ alkyl radicals. The term alkyl is used herein to include the alkyl portion of higher allyl radicals. Examples of dropwise synthetic anionic detergent compounds are sodium sulfates and potassium alkyls, in particular sodium sulfates and potassium alkyls obtained by sulfation of higher (C ₈ -C ₁₈ ) alcohols, for example, produced from tallow or coconut oil. _9- C ₂₀ ) Sodium and potassium benzenesulfonates, in particular linear secondary alkyl (C ₁₀ -C ₁₅ ) sodium benzenesulfonate: Sodium alkyl glyceryl ether sodium sulfate, in particular derived from higher alcohols and petroleum derived from tallow or coconut oil Sodium sulfates of esters of alcohols: coconut oil fatty acid monoglycerides and sodium sulfonates: sodium and potassium salts of sulfate esters of the reaction products of higher (C ₉ -C ₁₈ ) fatty alcohol-alkylene oxides (especially ethylene oxide): coco Reaction products obtained by esterifying fatty acids such as nitrate with isethionic acid and neutralizing with sodium hydroxide: fatty acids of methyltaurine Sodium and potassium salts of the de: alpha-olefin singer the materials, and paraffins derived by the reaction of sodium bisulfate (C ₈ -C ₂₀₎ with a base and then to produce a random sulfonate salt was reacted with SO ₂ and CI ₂ Alkanomonosulfates, such as those derived by decomposition, include olefin sulfonates, which are substances obtained by reacting olefins (particularly C ₁₀ -C ₂₀ alpha-olefins) with SO ₃ and then neutralizing and hydrolyzing the reaction product. .

Suitable soaps are soaps which are alkali metal salts of long chain C ₈ -C ₂₂ fatty acids such as tallow, coconut oil, palm kernel oil, palm oil or hardened rapeseed oil fatty acids or sodium soaps of these mixtures. Preferred anionic detergent actives are sodium (C ₁₁ -C ₁₅ ) alkylbenzene sulfonate and sodium (C ₁₆ -C ₁₈ ) alkyl sulfate.

Materials used as suitable nonionic detergents are reaction products of alkyl (C ₆ -C ₂₂ ) phenols and alkylene oxides (usually ethylene oxide), generally having 5 to 25 units of ethylene oxide (ie -EO) per molecule. Substances: Condensation products of aliphatic (C ₉ -C ₁₈ ) primary or secondary linear or branched alcohols with ethylene oxide (usually 60-EO), and products obtained by condensation of ethylene oxide with ethylene oxide to be. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides, and dialkyl sulfoxides.

Mixtures of detergent active compounds, such as anionic mixtures or mixtures of anions and nonions, may be used in the detergent composition. The latter is particularly useful for compositions used in automatic washing machines that do not allow foaming because they provide controlled antifoam properties.

A certain amount of amphoteric or zwitterionic detergent active compounds may also be used in the compositions of the present invention but are not preferred because they are relatively expensive. However, when amphoteric or zwitterionic detergent active compounds are used, they are used in small amounts in compositions based on synthetic anionic and / or nonionic detergent active compounds that are commonly used.

The detergent composition of the present invention also contains about 15-40% by weight, preferably 20-35% by weight of water-insoluble aluminosilicate cation exchange material.

The aluminosilicate may be crystalline or amorphous. Preferred aluminosilicate materials have the following unit formula (I):

M ₂ [(AiO ₂ ) _z (SiO ₂ ) _y ] _x H ₂ O

Wherein M is a calcium exchange cation, Z and Y are at least 6, the molar ratio of z to y is about 1.0-0.5 and X is at least 5, preferably about 7.5-276, in particular about 10-264 . The aluminosilicate material is preferably a crystalline form containing about 10-28%, in particular about 18-22%, water as the hydrated form.

The aluminosilicate ion exchange material is characterized by a particle diameter of about 0.1-10 microns, preferably about 0.2-4 microns. The term "particle diameter" refers to the average particle diameter of a given ion exchange material specified by conventional analytical methods such as microscopy using a scanning electron microscope. In addition, in the present specification, the aluminosilicate ion exchange material has a calcium ion exchange capacity of the material at least about 200 mg equivalent of CaCo _{3 water} hardness, generally about 300 mg equivalent / g-352 mg equivalent / g, based on anhydride based alumino silicate. It is characterized by.

In addition, in the present specification, the aluminosilicate ion exchange material has a calcium ion exchange rate of at least about 2 grains Ca ⁺⁺ / gallon / min per gallon of aluminosilicate (anhydride) based on the calcium ion hardness, and generally about 2 grains / Gallons / minutes / grams / gallons-6grains / gallons / minutes / grams / gallons. The most suitable aluminosilicates for adjuvant are those having a calcium ion exchange rate of at least 4 grains / gallon / min / gram / gallon.

Embodiments of the Invention The useful aluminosilicate ion exchange materials are commercially available and can be obtained naturally or synthesized. A process for the preparation of aluminosilicate ion exchange materials is described in US Pat. Synthetic crystalline aluminosilicate ion exchange materials useful in the present invention preferably utilize designated zeolite A, zeolite B, zeolite X zeolite HS and mixtures thereof. In a particularly preferred embodiment the crystalline aluminosilicate ion exchange material is zeolite A, the general formula of which is

Na ₁₂ [AIO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _x H ₂ O

Wherein X is about 20-30 factors, in particular about 27. Also suitable are zeolites X having the formula Na ₈₆ [AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] 276H ₂ O and zeolite HS having a color of Na ₆ [AIO ₂ ) ₆ (SiO ₂ ) ₆ ] 7.5H ₂ O. .

Na₃

2H₂O)이다.The detergent composition of the invention also contains citric acid or an alkali metal salt of citric acid in an amount of about 1-15% by weight, preferably 2-10% by weight of the composition. Preferred alkali metal salts of citric acid are sodium citrate, in particular trisodium citrate (C ₆ H ₅ O ₇

Na ₃

2H ₂ O).

Detergent compositions of the present invention may contain additives usually in amounts commonly used in textile laundry compositions together with the components described above. Such additives include foam promoters, such as alkanolamides (especially monoethanolamides derived from palm kernels and coconut fatty acids): foam inhibitors such as alkyl phosphates, silicones and waxes: sodium carboxymethyl cellulose (SCMC), polyvinylpyrrolidone Anti-redeposition agents such as (PVP) and cellulose ethers (e.g. methyl cellulose and ethyl hydroxyethyl cellulose): stabilizers such as ethylenediamine tetraacetate: textile phosphorus agents: inorganic salts such as sodium sulfate and sodium carbonate, etc. As the component, a fluorescent agent, a flavoring agent, an enzyme (for example, a protease, amylase and a lipase), a fungicide, a coloring agent, and the like are used.

Although not essential, the polycarboxylic acid polymer also preferably contains about 0.5-6% by weight of the total composition. The lollycarboxylic acid polymer herein is derived from unsaturated polycarboxylic acids such as maleic acid, citraconic acid, itaconic acid or mesaconic acid as the first unit and from ethylene, methylvinylether, acrylic acid or methacrylic acid as the second monomer. It is preferably selected from the derived copolymer polycarboxylic acids and salts thereof, the copolymer having an average molecular weight of at least about 10,000, preferably at least about 30,0000 and at least about 10 mole percent, preferably at least about 20 moles. It contains at least% polycarboxylic acid units. The polycarboxylic acid polymer may also be selected from homopolyacrylic and homopolymethacrylic polymers having a weight average molecular weight of about 1000 to about 100,000, preferably about 5000 to about 50,000. It is also possible to use the mixture.

Detergent bleach compositions of the invention are generally alkaline and advantageously have a pH of 8-11 (at 2-10 g / l) and an optimal pH of 8-9.

The pH of the wash liquor is 8.5 which is most suitable in terms of good bleaching power, cleaning power and enzymatic descaling. pH adjustment requires a buffer such as borax.

Detergent composition of the present invention is preferably supplied in the form of particles without flow, that is, powder or granules. The detergent composition can be prepared by known techniques commonly used in the manufacture of laundry compositions, but the spray-dried aqueous slurry containing the surfactant (s), aluminosilicate, and alkali metal salts of citric acid is spray dried to form a detergent base powder. It is preferred to add a heat sensitive component, including peroxybenzoic acid bleaching precursor, inorganic peroxides, enzymes and other desired components. Alternatively, the alkali metal salt of citric acid may be dry mixed separately from the spray-dried base powder. Bleach precursors and enzymes are preferably added as granule particles. It is preferable to obtain a composition having a water content of 15% or less, more preferably about 7-14% by weight at the time of preparing the composition.

The invention will now be illustrated by the following non-limiting examples.

Example 1

The aqueous detergent slurry was spray dried to form a detergent base powder composition (A) and then combined with the product composition (B) on the particles to prepare a particulate rinse detergent composition.

1%, 2%, 3%, 5%, 10% by weight of trisodium citrate was added with and without the addition of 30 minutes of tergotometer laundering, and washing experiments were carried out using the above-mentioned composition. The dose was 8 g per liter of 24 ° FH water at 40 ° C. and the pH was adjusted to 8.5.

The bleaching characteristics for black tea and red wine contamination were measured. The results are shown in Table I.

TABLE 1

Example 2

Bleaching power, washing power and protein decontamination (enzyme action) against black tea and red wine contamination were tested. The results are shown in Table 2.

TABLE 2

From the above results, it can be seen that trisodium stronate promotes the bleaching effect on black tea and red wine contamination without negative effects on washing power and enzymatic action (ie, protein decontamination).

Claims (6)

At least one detergent active material and (a) about 15-40% by weight of water-insoluble aluminosilicate cation exchange material (b) about 1-15% by weight of citric acid or alkali metal salt of citric acid (c) about 5-35% by weight of inorganic peroxide (d) A bleach composition for a rinse detergent containing about 1-10% by weight of a peroxybenzoic acid bleaching precursor. The detergent active material according to claim 1, wherein the detergent active material is selected from the group consisting of anionic, nonionic, amphoteric, zwitterionic, detergent compounds, and soaps and mixtures thereof. 20-35% by weight of the aluminosilicate cation exchanger -A bleaching composition for a rinse detergent containing 2-10% by weight of the citric acid or an alkali metal salt of citric acid. According to claim 1, wherein the peroxybenzoic acid precursor is a structural formula

B-rinse detergent composition, characterized in that the sodium P-benzoyloxybenzene sulfonate. The bleaching composition according to claim 1, wherein the alkali metal salt of stric acid is trisodium citrate. 2. The bleach composition of claim 1 wherein the composition has a pH of the solution (at 2-10 g / l) of 8-11. 6. The bleach composition of claim 5 wherein the pH of the solution is between 8-9.