JPH0267399A - Bleaching detergent composition - Google Patents

Abstract

PURPOSE: To effectively bleach an oxidizable stain at a low washing temperature by selecting a specified compound as bleaching activating agent in an alkaline bleaching detergent composition containing a surface active agent, a detergent builder, a proteolytic enzyme, a peroxide compound and the bleaching activating agent.

CONSTITUTION: The bleaching detergent composition contains a surface active agent (e.g. sodium alkylbenzenesulfonate, aliphatic alcohol ethoxylate or the like), a detergent builder (e.g. alkali sodium silicate, ethylenediamide tetraacetate or the like), a proteolytic enzyme (e.g. Savinase or the like), a peroxide compound (e.g. sodium perborate tetrahydride or the like) and a bleaching activating agent which is 1,2-diacyloxybenzene-3,5-disulfonate represented by the formula [R, R¹ are each 1-10C alkyl or 6-10C (substituted) phenyl; M is H, alkali (earth) metal, or (substituted) ammonium].

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to bleaching detergent compositions, particularly so-called low temperature bleaching detergent compositions of the type in which the bleaching system functions during use by the production of organic peroxy acids. Such compositions essentially contain peroxides, e.g. persalts such as sodium perborate,
and organic compounds (so-called "bleach activators" or "bleach precursors"), which can react with peroxides in solution at relatively low temperatures to form organic peroxyacids, It is effective for regular low-temperature bleaching in commercial washing (2) and dry cleaning operations.

When used for laundry laundry, such compositions often further contain oxygen, particularly proteases, which aid in the removal of proteolytic stains.

The term "peroxide" is used herein to refer to those decompositions that cause active oxygen in solutions, in particular inorganic "AM" compounds such as alkali metal perborates, persilicates, percarbonates and perphosphates, to be separated by T1. Bleach detergent compositions containing such inorganic peroxides and their organic bleach activators are known in the art. Various materials have been proposed in the art as bleach activators or bleach precursors. Ta.

Generally, these are carboxylic acid derivatives, for example (UK Patent Nos. 836,988 and 9'70,950 II
esters (such as those described in the British Patent No. 9)
No. 07,356; No. 855.735; No. 1,246;
339 and US Patent No. 4,128,494), and acylamides (such as those described in Canadian Patent No. 844,481).

Other more recent patent publications disclosing bleaching active agents include, for example, U.S. Pat. No. 4,283,301;
U.S. Pat. No. 4,412,934 and EP-A-0
There is 120591.

A typical bleach activator in the concept of said patent publication is N
, N, N', N'-tetraacedelethylenediamine (
1ΔED>, sodium acetoxybenzenesulfonate (SABS>), sodium benzoyloxybenzenesulfonate (SBBS), sodium n- and iso-nonanoyloxybenzenesulfonate (SNOBS and iso-8NOBS).

With respect to the general trend of still low clothes washing temperatures, for example below 40° C., there are a series of incentives for further improvements on the bleaching performance of clothes washing compositions without detrimentally affecting enzyme action. There is also a series of demands to further develop new and alternative formulations of laundry detergents that meet the above requirements.

DESCRIPTION OF THE INVENTION Certain diacyloxybenzene sulfonate salts, defined below, are highly effective at removing oxidizable stains on clothing at temperatures of 540°C when added to an aqueous liquid containing an alkaline hydrogen peroxide source. It was found that it bleaches. These diacyloxybenzene sulfonate compounds can be used as bleach activators in alkaline detergent compositions containing peroxides and enzymes to eliminate a wide variety of smudges during home or laundry laundering at temperatures below 40°C. Forms a low temperature bleach detergent composition that is highly effective in removing 1
qru.

Bleach activators for use in the present invention are of the formula: (wherein R and R1 are each independently an @ chain or non-linear alkyl group containing 1 to 10 carbon atoms, or 6 to 10
a phenyl group or a substituted phenyl group containing 1. 1,2-diacyloxybenzene-3,5-disulfonate represented by alkali metal, alkaline earth metal, ammonium or substituted ammonium).

These include 1,2-dibenzoyloxybenzene-3, which is described in West German Patent Application No. 2,817,858 as having antibacterial properties, in the form of a mixture with sodium percarbonate.
All compounds other than nibutrium 5-disulfonate are new compounds.

Accordingly, the present invention provides an improved alkaline detergent composition, particularly for laundry laundry, comprising a surfactant, a detergent builder, a proteolytic enzyme, a peroxide and a bleach activator, the bleach activator being of the formula : (wherein R and R1 are each independently a straight-chain or non-linear alkyl group containing 1 to 10 carbon atoms, or a phenyl group or substituted phenyl group containing 6 to 10 carbon atoms, ; M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium).

R and R1 may be the same group or different groups. Preferably R and R1 are the same.

In a preferred compound, R and R1 are phenyl groups.

A p-tert-butylphenyl group, or a linear or non-linear C6-C8 aryal group, and M is an alkali metal, preferably sodium.

Therefore, the following ten compounds are examples of bleach activators in the present invention, such as 5-di(1,2-dibenzoyloxy disodium benzenesulfonate) 3.5-dis(1,2-dinonanoyloxybenzene-sulfonate disodium) 5-dis(12-diacetoxybenzene-acid disodium) 5-disulfone 2-di-tert.

Butylbenzoyloxy-3.5 Diacyloxybenzenedisulfone same as in this specification 1 m
are more weight effective than their corresponding monoacyloxybenzene sulfonates, which means that when equal weights they exhibit more effective bleaching action, especially at their R-suitable pt-+ values. do. Similar isomeric compounds, such as 13-diacyloxybenzene-4,6-disulfonate and 1,3-diacyloxybenzene-4,5-disulfonate, are less effective or difficult to synthesize and are not suitable for the present invention. is outside the range of

Each of the bleach activators defined herein can be used as a single compound in the bleaching detergent compositions of the present invention; however, if desired, a mixture of two or more compounds,
For example (I) + (IV) or (I) + NV) + - (V
) or (II) + (V) may be used. The use of such mixtures is believed to be beneficial with respect to overall stain removal properties and is also within the scope of the present invention.

Advantageously, the alkaline detergent compositions of the present invention comprising a bleach activator as described by Suimei Im have a pH of 2 to 5 within the range of 8.5 to 10.5
g/j! Indicates the solution pH; a pH value of about 8.5-9.0 is optimal and preferred.

Peroxides are well known in the art. These include alkali metal peroxides, organic peroxide bleaching compounds such as peroxide, inorganic persalt bleaching compounds such as alkali metal perborates, percarbonates, perphosphates and persulfates. Mixtures of two or more such compounds are suitable. Particularly preferred is sodium perborate tetrahydrate, especially sodium perborate-hydrate. Sodium perborate hydrate is preferred because it exhibits excellent storage stability while being readily soluble in aqueous bleaching solutions.

Typically, the equivalent omega ratio of hydrogen peroxide (or an equivalent amount of peroxide producing T]202) to precursor is from 0.5:1 to about 2
0:1, preferably 1:1 to 15:1, most preferably 2:1 to 10:1.

Detergent formulations of the invention also generally contain surfactants and detergent builders.

For J3 in the formulation of the present invention, the bleach activator is about 0.1 to 2
0% by weight, preferably 0.5-10% by weight, especially 1-7%
peroxide bleaching compounds, at levels in the range of 5x51%;
or tetrahydrate of sodium perborate (usually in the range of about 2 to 40%, preferably about 4 to 30%, especially about 10 to 25% by weight). You may.

The surfactant may be a natural or synthetic substance selected from anionic, nonionic, amphoteric, zwitterionic, cationic active agents and mixtures thereof. A large number of suitable activators are commercially available, see the literature, e.g.
ace Active Agents and Dete
rgents” (Volumes I and ■, 5ChWartZ,
Perry and BerCh). The total level of surfactants may be up to 50% by weight of the composition, preferably from about 1 to 4011%, most preferably from 4 to 251 m%.

Synthetic anionic surfactants are typically water-soluble alkali metal salts of organic sulfuric and sulfonic acids having alkyl groups containing about 8 to 22 carbon atoms, where the term alkyl refers to higher aryl groups. It is used including an alkyl moiety.

Examples of suitable synthetic anionic detergent compounds include notorium and ammonium alkyl sulfates, especially higher <C-
018) those obtained by sulfating alcohols (e.g. produced from tallow or coconut oil); sodium and ammonium alkyl (09-C2o) benzene sulfonates, especially sodium linear linear alkyl (C1o-C15) benzenes Sulfonates; sodium alkyl glyceryl ether sulfates, especially esters of higher alcohols derived from tallow or coconut oil, and esters of synthetic alcohols MS derived from petroleum; sodium cocosseed oil fatty acid monoglyceride sulfates and sulfonates : Higher (C9-Cl8) fatty alcohol alkylene oxide, especially ethylene oxide reactant VAN
Sodium and ammonium salts of esters; reactants of fatty acids such as coconut fatty acids which are engineered with isethionic acid, esterified and neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of medyl taurine; alpha olefins ( Those derived by reacting C to C2o) with sodium bisulfite,
M
Alkane monosulfonates, such as sodium and ammonium C-012 dialkyl sulfosuccinates;
(Used to describe a substance produced by reacting with 3 and then neutralizing and hydrolyzing the reactant).

Preferred anionic detergent compounds include (C11-C15) norium 4-benzenesulfonate, (C16-
C18) alkyl, sodium sulfate, and (016-C
l8) Sodium alkyl ether sulfate.

Examples of suitable non-ionic surfactants which may preferably be used with anionic surfactants include alkylene oxides, usually ethylene oxides and alkyl (C6-C22)
Reactant with phenol (generally 5-25 [0, i.e. 5-.25 units of ethylene oxide per molecule): aliphatic (C8-Cl8) primary or secondary straight or branched chain alcohol and oxidation 1 Examples include condensates of dylene, (generally 6 to 30E O), and ethylene oxide, and condensates of propylene oxide and reactants such as ethylenediamine. The so-called nonionic surfactants include alkyl polyglycosides and long-chain tertiary amine oxides.

There are long chain tertiary phosphine oxides and dialkyl sulfoxides.

Large amounts of amphoteric or zwitterionic surfactants may be used in the compositions of the present invention, but are generally undesirable because of their relative expense. If any amphoteric or zwitterionic detergent compounds are used, they are generally in small amounts in compositions based on the most commonly used synthetic anionic and nonionic actives.

As above, soaps may be included in the compositions of the present invention, preferably at levels less than 25% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures with nonionic compounds or mixed synthetic anions and nonionic compounds. The soap used is preferably saturated or unsaturated C10"C2
4 fatty acid salts, or less preferably potassium salts, or mixtures thereof. The strength of such soaps can vary from about 0.5% to about 25% by weight, but generally less, about 0.5% to about 5%, is required to suppress foaming.
It is "-min" in weight %. To produce beneficial cleaning effects,
About 2 to 201% of soap is used, especially about 5 to 10% of soap. This is particularly beneficial in compositions for use in hard water where the soap acts as a supplemental builder.

Detergent builders may be selected from 1) calcium sequestering agents, 2) precipitating materials, 3) calcium ion exchange materials, and 4) mixtures thereof.

Examples of calcium-sequestering compounds include alkali metal polyphosphates such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; Alkali metal salts of acids; and polyacetal carboxylates (U.S. Pat. Nos. 4.144.226 and 4.146.49)
(described in No. 5).

Examples of precipitating virgoos include sodium orthophosphate, sodium carbonate, and long chain fatty acid soaps.

Examples of calcium ion exchangers include various types of water-insoluble crystals or amorphous aluminolytes, among which zeolites, such as zeolite
, Y and A are the most known representative substances. In particular, the compositions of the invention may be prepared from any organic or mineral-free building blocks such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, putrium salts of nitrilotriacetic acid, citric acid It may contain sodium, carboxymedyl malonate, carboxymebyl quaternary succinate, and water-insoluble crystalline or amorphous aluminosilicate builders, or mixtures thereof.

These builders may be present, for example, at a level of 5 to 80%, preferably 10 to 60%.

Proteolytic enzymes suitable for use in the present invention are generally solid, catalytically active proteins that, during the hydrolysis reaction, degrade the protein form of the ooze when present in the fiber. or change. Any suitable source such as plants, a
They may be produced from FJ, bacteria, or yeast.

Proteolytic enzymes, or proteases, of different nature and origin and exhibiting activity in different pH ranges from 4 to 12 are:
are useful and can be used in the compositions of the present invention. An example of a suitable proteolytic enzyme is subtilisin,
This is subtilisin HaXataSe■ (Gist-
Brocades N, V, Delft Netherlands) and ^1calase■ (Novo tntlu
to stri/SCopenhagen, Denmark)
commercially available as B, 5ubtilis and B
, 1 from a specific strain of P. licheniformis! I get caught.

Particularly suitable are proteases obtained from Bacillus strains which exhibit maximum activity over the entire pH range from 8 to 12 and are commercially available, for example, from Novo InduStri^/S under the trade names Esperase ■ and 5avinase ■. The manufacture of these and similar enzymes is described in British Patent No. 1,243,784.

Other commercially available 10-teases include niazusasc (
Available from Showa Denko in Japan), Optimase■
(West Germany 11annover, Miles Kali-
Chemie), and 5uperase■ (US Pfi
zer).

The amount of proteolytic enzymes generally used in the compositions of the invention may range from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, depending on their activity. They are generally prepared using granules, 7@lyls, or riarumes J.
It is included in the form of

Apart from the compounds already mentioned, the detergent compositions of the invention may contain any conventional additives in amounts commonly used in laundry detergent compositions. Examples of these additives include:
Foam promoters such as alkanolamides, especially monoethanolamides derived from balm and coconut fatty acids; foam suppressors such as alkyl phosphates and silicones; anti-reprecipitation agents such as sodium carboxymethyl cellulose and alkyl or substituted alkyl lerulose ethers. peroxide stabilizers such as ethylenediaminedetraacetic acid, ethylenediaminetetra(methylenebosphonic acid) and diethylenediaminebenzene (methylenephosphonic acid); inorganic salts such as sodium sulfate; No light agents, no fragrances, no bactericides, no colorants,
as well as other enzymes such as cellulose, liver 12. Examples include amylase.

Other useful additives include polymeric materials such as polyacrylic acid, polyethylene glycol.

and copolymers of (meth)acrylic acid and maleic acid, which may also be included to function as auxiliary builders with any primary detergent builders such as polyphosphates and especially aluminosilicates.

Specific examples of lipases include HLlmlCOlaLan
uginosa or Thermomyces Lanu
fungal lipase derived 1':1 from C. ginosa, and C.
There are bacterial lipases that react positively with antibodies of lipapi from hromobacter Viscosum.

Functional fluorescent agents used herein are, for example, of the -diaminosdilbene/cyanuric chloride type, such as Bl
ankophor@) M B B 1]: those of the disbourylbenzene type, such as Tinopal CBS and Ti nopa I BLS: and those of the triazole type, such as Blankophor@B HC and T
There is i'nopal■RBS.

Blankophor(p)B HC and Ti nop
The combined use of a l■BLS is preferable for cotton fibers, and T
inopa l■RBS is preferred for nylon IIfl.

Blankophor and Ti no pal are registered trademarks.

The alkaline detergent compositions of the present invention may be present in any suitable state of aggregation, for example as a solid or a liquid. However, they are preferably present in free-flowing particulate form, e.g. powder or granule form, although they can be prepared by any known technique commonly used by manufacturers of such cleaning compositions, e.g. An aqueous slurry consisting of a surfactant and a builder is spray dried to form a detergent base powder, which is combined with heat-sensitive ingredients such as a bleach activator, one or more enzymes, a peroxy compound, and optionally any convenient additives. It can be produced by adding some other ingredients as desired; 2) dry blending; or 3) dry blending/wet blending.

Generally, and for reasons of improved stability and handling, it is preferred to add the bleach activator and enzyme as granulated particles.

In another embodiment, the alkaline detergent composition of the present invention is in the form of a non-aqueous liquid detergent composition.

A detergent base powder of the composition named below was prepared by spray drying.

Composition Sodium alkylbenzene sulfonate Fatty alcohol/7 ethoxylate Sodium alkali Silicate (1:2) Sodium triphosphate Proxymethyl cellulose Evenediamine tetraacetate (EDTA) Fluorescent agent Sodium sulfate The following series were used for the cleaning test: The following substances were used.

Series I heavy
Amount % (A> (B) (C) (D) Detergent base 75.0075.0075.007
5.00 Bleach Activator: Compound (I) BBS 150-3 NOBS ■ Eel Water 3.83 3.21 5.72 to 100 Series ■ Weight n] % Bleach Activator Compound (I) BBS Iso-3 NOBS AED Water 3 .83 3.21 - 6.6 up to 100 5.72 This ethylenediaminetetra-(methylenephosphonic acid) washing as described below except that the bleach activator level used in both series was maintained at a pH of 9.5. Under conditions, the Seriese formulation was precalculated to yield 7 reflectance units (ΔR460'') on a standard black tea stain test cloth.

The sodium perborate level in series ■ was kept constant at 14% by weight, while this level was maintained in series ■ at a 1:1 equivalent ratio of perborate to activator in compositions A-D. Changed.

4g/j! 15°F in the presence of matter All 4 in the water
Washing was performed at a constant temperature of 0°C. After adding all the cleaning ingredients except the bleach activator, the cleaning pH was adjusted to pH 8.5 with sulfuric acid.

Washed for 20 minutes using a standard black tea stain test cloth, RA
Cleaning with the GtJ■ (spaghetti sauce) stain test cloth was limited to 10 minutes as the stain came off relatively easily. Black tea is a typical hydrophilic stain, and RAGU■
is used as a typical hydrophobic stain.

RAGUL, 40% Test Fabric RAGtJ Spaghetti Sauce (Available in the US)
4 d of toluene was added to rrdl and shaken vigorously. After centrifugation for approximately 15 minutes, the clear red-orange supernatant toluene solution was carefully poured into another bottle. This is 10×15C
I! The solution was applied using a 150-layer suspension equivalent to a 1-sized clean cotton cloth and waited in a dark place until the toluene evaporated.

Note: This stain is bleached by both light and oxygen.

Therefore, it is necessary to use it as soon as possible after the stain appears, and it is also necessary to wrap it in light-blocking paper and store it in a refrigerator under nitrogen. Stains older than 7 days should be discarded.

The entire cleaning experiment was repeated three times and the resulting average reflectance values are shown in the table below.

Table ■ Results of bleaching/cleaning test at 40℃ (ΔR460”) (
A) (B) (C3 (D) The result is that the white performance is 11.1 17.1 5.2 19.31
1.5 11.2 3.3 11.57.
8 12.6 2.7 9.06.0
10.7 3.7 8.9 Clearly the low temperature source of the material of the invention (Δ) is superior to other materials (B), (C) and (D) containing bleach activators of the prior art. It shows that

Bottle J192 Detergent base powders with the following names were prepared by spray drying: Composition 1a Parts by weight Sodium alkylbenzenesulfonate 6.0 fatty alcohols/7 ethoxylates 4.0 fatty alcohols/3 ethoxylates 3 .0 alkali sodium silicate (
1:2) 6.0 Sodium tripolyphosphate
25.0 mark TA
0.1 Sodium carboxymethylcellulose polyacrylate polymer 1.0 Sub-components (fragrance, fluorescent agent, etc.) 1.5 Sodium sulfate (+ water) Up to 80.0 Use this base powder to make the following alkaline bleaching detergent composition was prepared and used in the cleaning experiment.

Composition "DanX" Dan1 human-e detergent base Sodium perborate hydrate bleach activator Dequest■2041 Savinase■4. OI Granules *The bleach activator used is a compound SB[3S was used as a comparison.

80.0 1.6 5.0 0.4 1.0 (I) 80.0 13.0 5.0 0.4 1.0 Met.

Standard black tea stain.

Protein stain and RAGLJ L, sample 59/j on the test cloth! 18° for 15 minutes at a substance concentration of H 40℃ constant temperature cleaning conditions in water]; ■Erootometer in progress in, Do these compositions contain bleach activators? using things, Conducted two series of cleaning experiments did.

1 series is washed p) -18.5.

H9 The other series does not show its results below: ([) 10 Compound (I) (E) - Compound (I) 5.4 25.3 30.0 0.2 26.2 9.7 ”tan Σ Anti-Japanese drunken mouth Cyu + compound <I) +5BBS - activator 6.0 2B, 7 3B, 5 5.9 25
．． 6 16.24.7 26.8 27.4
6.4 27.0 8.40.9 23.4
8.6 0.6 25.4 7.5 Ko Zheng 1! -Pa'-7-4 Ji-hi Innote 5/Ma7゜

Claims (8)

[Claims] (1) An alkaline bleach detergent composition containing a surfactant, a detergent builder, a protease, a peroxide compound, and a bleach activator, where the bleach activator has a formula: ▲Mathematical formula, chemical formula, table, etc.▼ (Formula in which R and R^1 are each independently a linear or non-linear alkyl group containing 1 to 10 carbon atoms, or a phenyl group or substituted phenyl group containing 6 to 10 carbon atoms; H, alkali metal, alkaline earth metal,
ammonium or substituted ammonium). 2. The bleach detergent composition according to claim 1, wherein the bleach activator is 1,2-dibenzoyloxybenzene-3,5-disulfonic acid disodium salt. (3) The bleach detergent composition according to claim 1, wherein the bleach activator is 1,2-di-tert, butylbenzoyloxy-3,5-disulfonic acid disodium salt. (4) The bleaching detergent composition according to claim 1, wherein R and R^1 are linear or non-linear C_6 to C_8 alkyl groups. (5) The composition contains 2-40% by weight of a peroxide-based bleaching compound and 0.1-20% by weight of a bleach activator, with a ratio of peroxide to bleach activator of 0.5:1-20:1. The bleaching detergent composition according to any one of claims 1 to 4, characterized in that the bleaching detergent composition is contained in an equivalent ratio within a range. (6) A bleaching detergent composition according to any one of claims 1 to 5, characterized in that the composition exhibits a pH of 8.5 to 10.5 in a 2 to 5 g/l solution. (7) The bleaching detergent composition according to claim 6, wherein the pH of the solution is 8.5 to 9.0. (8) The composition is 2 to 20 Anson per 1 kg of total substance.
A bleaching detergent composition according to any one of claims 1 to 7, characterized in that it has a proteolytic activity of .