JP2004211080A - Bleach detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching detergent composition having enhanced bleaching detergency.
SOLUTION: (a) 0.1 to 20% by mass of a peroxide which generates hydrogen peroxide in an aqueous solution, and (b) 0.05 of a peracid precursor which reacts with hydrogen peroxide to generate an organic peracid. (C) 1 to 30% by mass of a nonionic surfactant having 0 to 15 moles of alkylene oxide in the molecule, (d) an enzyme having lipase and / or esterase activity, and (e) an enzyme having an esterase activity. A bleaching detergent composition containing 1 to 30% by mass of a nonionic compound having 20 to 500 mol of alkylene oxide.
[Selection diagram] None

Description

  The present invention relates to a bleaching detergent composition and a washing method particularly suitable for textile products.

  Detergent compositions are strongly directed to higher densities and lower usage in consideration of consumer convenience and environmental considerations. In addition, consumer demand for “easy washing” and “washing clothes carefully” and responding to the environment, energy, and economy have led to the trend toward water saving, low-temperature washing, and shortening of washing time. is there.

  With changes in the living environment, the stains that adhere to clothing and the like in daily life are also diversifying, and washing with ordinary detergents alone will prevent blood stains, food stains, so-called stain stains such as plant stains, and lipophilic stains. Detergency is not enough. Further, in particular, collar and cuff stains cannot be completely removed by ordinary washing, and such residual sebum causes yellowing of clothing during storage.

  Since bleaching agents are very effective for stains and the like, it is common to add bleaching components to detergents. Bleaching components are roughly classified into oxygen-based and chlorine-based. Examples of the chlorine type include hypochlorous acid and dichlorocyanuric acid. These have problems in stability, smell, and the like, are not suitable for blending detergents, and have to be nervous when used for colored or patterned clothing because of their strong bleaching power. Oxygen bleaches have a slight decrease in bleaching power at room temperature compared to chlorine bleaches, but do not lose color when applied to colored or patterned clothing, do not damage the fabric, and yellow. It is widely used as a cleaning agent because of its lack. Further, in order to improve the bleaching performance, an organic peracid precursor or the like is used in combination.

  Nonionic surfactants used as detergent bases have good hard water resistance, outstanding washing power for oily stains such as sebum stains, and very good biodegradability. Therefore, the technical development of detergents containing nonionic surfactants has been actively conducted.

  However, in a bleaching system using a detergent containing a nonionic surfactant and an organic peracid precursor, the organic peracid precursor has a high affinity for the nonionic surfactant and is contained in the micelle of the nonionic surfactant. There is a problem that the amount of peracid is reduced, and the bleaching power is greatly reduced, because the compound is strongly taken in and hardly comes out of the micelle. For this reason, studies have been made to improve the bleaching detergency of a detergent containing a nonionic surfactant and an organic peracid precursor. For example, improvement in bleaching power by containing a sequestering agent (for example, see Patent Documents 1, 2, and 3) is known. However, these methods reduce the bleaching power by sequestering metal ions in a washing bath. It is to prevent.

  In addition, an enzyme having lipase and / or esterase activity has been studied to be added to a detergent in order to help remove triglyceride and fatty ester-based stains (for example, see Patent Documents 4, 5, and 6). In addition, nonionic compounds having 20 to 500 moles of alkylene oxide in the molecule have been studied for addition to detergents as anti-soil refining agents and detergent particle property improvers (for example, Japanese Patent Application Publication No. Collection (powder detergent for clothing).).

  However, due to the synergistic effect exerted by combining an enzyme having lipase and / or esterase activity with a nonionic compound having 20 to 500 moles of alkylene oxide in the molecule, organic peracid is efficiently produced and bleached. The effect of enhancing detergency was not known.

In addition, a bleaching method for producing a peracid by reacting an enzyme having lipase and / or esterase activity with a specific ester and a peroxygen source is known (for example, see Patent Document 7). I couldn't say.
JP-A-9-3497 JP-A-10-316996 JP-A-11-35978 JP-A-9-194885 Japanese Patent Publication No. Hei 8-511826 JP-A-63-16087 JP-A-62-292898

  An object of the present invention is to provide a bleaching detergent composition and a cleaning method which exhibit excellent cleaning performance against yellowish stains such as sebum stains and underwear.

  By combining an enzyme having lipase and / or esterase activity with a nonionic compound having 20 to 500 moles of alkylene oxide in the molecule, the present inventors have found that organic peracids are efficiently produced and the bleaching detergency is greatly increased. The present inventors have found that the present invention is significantly enhanced and completed the present invention.

  That is, the present invention provides, as a means for solving the above problems, (a) 0.1 to 20% by mass of a peroxide which generates hydrogen peroxide in an aqueous solution, and (b) reaction with hydrogen peroxide to produce an organic peracid. (C) 0.05 to 10% by mass of a peracid precursor represented by the following general formula (I), (c) 1 to 30% by mass of a nonionic surfactant having 0 to 15 mol of alkylene oxide in the molecule, A) a bleaching detergent composition containing an enzyme having lipase and / or esterase activity, and (e) 1 to 30% by mass of a nonionic compound having 20 to 500 mol of alkylene oxide in the molecule.

[Wherein, R ₁ is a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group having 4 to 18 carbon atoms, an acyl group having 4 to 18 carbon atoms, or a compound represented by the following general formula (II) ) Represents a group represented by

(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group, alkenyl group or acyl group having 1 to 18 carbon atoms;
R ₃ represents a linear or branched alkylene group having 1 to 8 carbon atoms;
p represents 0 or 1;
R ₄ represents a phenylene group which may be substituted with a linear or branched alkylene group having 1 to 8 carbon atoms or a linear or branched alkyl group having 1 to 5 carbon atoms;
A represents a linear or branched alkylene group having 1 to 4 carbon atoms;
q is an average number of added moles of alkylene oxide, and represents a number of 0 to 100, and q A's may be the same or different)
L represents a group represented by the following general formula (III), (IV), (V), or (VI).

(Wherein, M represents a hydrogen atom or a cation forming a water-soluble salt, and R ₅ and R ₆ represent a linear or branched alkylene group having 1 to 8 carbon atoms)]
Further, the present invention provides, as another means for solving the problems, (a) a peroxide which generates hydrogen peroxide in an aqueous solution, and (b) a compound which reacts with hydrogen peroxide to form an organic peracid. (D) lipase and / or esterase in aqueous washing using a peracid precursor represented by the following formula (c) and a bleaching detergent containing a nonionic surfactant having 0 to 15 mol of an alkylene oxide in the molecule. The present invention provides a cleaning method using an enzyme having activity and (e) a nonionic compound having 20 to 500 mol of an alkylene oxide in a molecule as a bleaching agent.

  The composition of the present invention comprises, together with the components (a) to (c), (d) an enzyme having lipase and / or esterase activity, and (e) a nonionic compound having 20 to 500 mol of alkylene oxide in the molecule. By using in combination, the organic peracid is efficiently produced, so that the bleaching detergency is drastically enhanced.

<(A) component>
The composition of the present invention contains, as the component (a), one or more compounds selected from compounds that release hydrogen peroxide in an aqueous solution.

  The component (a) includes carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide And adducts. Among these, carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct are preferable, and sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable.

  The component (a) is preferably coated with an inorganic compound, an organic compound, or the like from the viewpoint of storage stability. Examples of the inorganic compound include sodium carbonate, sodium sulfate, magnesium sulfate, magnesium silicate, magnesium chloride, magnesium oxide, and sodium silicate. Examples of the organic compound include polyethylene glycol, polyvinylpyrrolidone, and hydroxypropyl cellulose.

  When used as particles containing the component (a), the amount of the inorganic compound or organic compound used for coating is preferably 5 to 20% by mass in the particles in terms of stability and solubility. In addition, conventionally known stabilizers, dissolution promoters, chelating agents and the like may be contained in the particles. Among these stabilizers and the like, chlorides, urea, anionic surfactants and nonionic surfactants are preferable from the viewpoint of solubility, and their contents are respectively 0.1 to 5 in the particles. % By mass is preferred.

  When a component coated with an inorganic or organic compound or the like is used as the component (a), it can be produced, for example, by applying the method described in Examples of JP-A-59-196399.

  The content of the component (a) in the composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, further preferably from 1 to 8% by mass in terms of cleaning performance. It is particularly preferably 2 to 7% by mass.

<(B) component>
The composition of the present invention contains, as a component (b), a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid.

  As the peracid precursor of the component (b), those represented by the above formula (I) are preferable.

In the general formula (I), R ₁ is a straight-chain or branched-chain alkyl group having 4 to 18, preferably 7 to 18, more preferably 10 to 13 carbon atoms, alkenyl, in terms of washing performance. In addition to the group and the acyl group, an aryl group is preferred, and an alkyl group is more preferred.

  L in the general formula (I) is preferably a group represented by the general formula (III) or (IV) (particularly, a group represented by (III)). M includes an alkali metal ion, an alkaline earth metal ion, an ammonium salt, an alkanolamine salt, and the like. Among them, a sodium ion and a potassium ion are preferable, and a sodium ion is particularly preferable.

  In the composition of the present invention, the component (b) is preferably in the form of particles containing the component (b) in order to enhance stability. The amount of the component (b) in the particles containing the component (b) is preferably 1 to 80% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass.

  In order to improve the solubility of the component (b) in a washing bath, the particles containing the component (b) include at least one selected from polyoxyalkylene alkyl ethers, alkyl sulfates and polyoxyalkylene alkyl ether sulfates. Of the surfactant can be blended preferably in an amount of 50% by mass or less, more preferably 1 to 45% by mass, and still more preferably 2 to 40% by mass.

  As the polyoxyalkylene alkyl ether, those in which ethylene oxide and propylene oxide are added in a block shape are preferable, the average number of moles of ethylene oxide added is preferably 3 to 20, particularly 4 to 15, and the average number of moles of propylene oxide added is 1 to 10, Particularly, 2 to 7 are preferable. The alkyl group preferably has 10 to 18 carbon atoms, particularly preferably 12 to 16 carbon atoms.

  As the alkyl sulfate, a sodium salt having 10 to 18 carbon atoms is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable.

  As the polyoxyalkylene alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having 10 to 18 carbon atoms in the alkyl group is preferable, and a sodium salt is preferable. Here, the average degree of polymerization of polyoxyethylene groups (hereinafter referred to as EOp) is preferably from 1 to 10, particularly preferably from 1 to 5, particularly preferably polyoxyethylene (EOp = 2 to 5) sodium lauryl ether sulfate, polyoxyethylene (EOp = 2 to 5). 5) Sodium myristyl ether sulfate is preferred.

  The particles containing the component (b) may be blended with a binder selected from polyoxyethylene and a fatty acid as a component for facilitating formulation.

  As polyoxyethylene, those having an average molecular weight of 2,000 to 20,000, more preferably 4,000 to 10,000, and particularly preferably 4,000 to 8,000, are preferable. Fatty acids are preferably those having 8 to 20, more preferably 10 to 18, and especially 12 to 18 carbon atoms, and these may be in the form of sodium or potassium soap. The binder is used in the particles containing the component (b) in an amount of preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 20% by mass.

  If desired, the composition of the present invention may further contain an acidic substance for the purpose of improving the stability of the particles containing the component (b).

  As the acidic substance, organic carboxylic acids are preferable, and at least one selected from succinic acid, maleic acid, fumaric acid, citric acid, glycolic acid and p-hydroxybenzoic acid is particularly preferable. The compounding amount of such an acidic substance is preferably 20% by mass or less, more preferably 1 to 15% by mass, and still more preferably 1 to 10% by mass in the particles containing the component (b).

  The particles containing the component (b) can be obtained by mixing the above components by a desired method and then granulating the mixture with a usual granulator. Particularly, the component (b) and the surface activity for improving the solubility can be obtained. A method in which part or all of the agent is mixed first, and then a binder or the like is added is preferable. It is preferable that the binder is added after being melted in advance at 40 to 100 ° C, more preferably 50 to 100 ° C, particularly 50 to 90 ° C.

  The granulation method is preferably an extrusion granulation method, and is preferably a granulated product having an average particle diameter of 500 μm to 5000 μm, particularly 500 to 3000 μm. In addition, tableting by a briquetting machine can be applied as a preferable granulation method.

  The content of the component (b) in the composition of the present invention is from 0.05 to 10% by mass, preferably from 0.05 to 5% by mass, and more preferably from 0.1 to 3% by mass in terms of cleaning performance. It is more preferably, 0.3 to 2% by mass, and particularly preferably 0.5 to 1.5% by mass.

<(C) component>
The composition of the present invention contains a nonionic surfactant having 0 to 15 mol of alkylene oxide in the molecule as the component (c).

  As the component (c), sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, fatty acid alkanolamide, polyoxyalkylene alkyl (C8-20) ether, alkyl glycoside, polyoxyalkylene Alkylene alkyl (C8-20) phenyl ether;

  Among them, sucrose fatty acid esters, sorbitan fatty acid esters, fatty acid alkanolamides, polyoxyalkylene alkyl (C8-20) ethers and alkyl glycosides are preferred, and polyoxyalkylene alkyl ethers are more preferred.

  In particular, from the viewpoint of cleaning performance, as the component (c), an alcohol having 10 to 18 (preferably 10 to 14) carbon atoms is mixed with 4 to 15 mol (more preferably 6 to 15 mol) of an alkylene oxide such as ethylene oxide or propylene oxide. 13 mol) added polyoxyalkylene alkyl ether is preferred.

  The content of the component (c) in the composition of the present invention is from 1 to 30% by mass, preferably from 3 to 25% by mass, more preferably from 5 to 20% by mass, and still more preferably from 8 to 30% by mass in terms of cleaning performance. 18% by mass.

  In terms of cleaning performance, the component (c) in the surfactant equivalent described in JIS K3362: 1998 is preferably at least 10% by mass, more preferably at least 30% by mass, and even more preferably at least 50% by mass.

  It is preferable to use an anionic surfactant together with the component (c) from the viewpoint of cleaning performance against various kinds of stains, and the mass ratio of the component (c) to the anionic surfactant is 1/9 to 9/1. Is more preferable, 3/7 to 9/1 is still more preferable, and 5/5 to 9/1 is particularly preferable.

<(D) component>
The composition of the present invention contains a lipase and / or an enzyme having an esterase activity as the component (d).

  The component (d) is preferably blended as particles containing the component (d) from the viewpoint of stability.

  The content of the component (d) in the composition of the present invention is preferably 0.002 to 10 KLU / mg, and 0.005 to 10 KLU / mg, from the viewpoint of efficiently producing an organic peracid by synergistic action with the component (e). -10 KLU / mg is more preferred, and 0.005-5 KLU / mg is even more preferred.

  LU (lipase unit) is the amount of lipase produced per micromol of fatty acid that can be titrated per minute at a constant pH under the following conditions.

Temperature: 30 ° C
pH: 9.0
Substrate: emulsion of 3.3% by weight of olive oil and 3.3% by weight of gum arabic in the presence of 13 mmol / l Ca ²⁺ Buffer: 20 mmol / l NaCl in 5 mmol / l Tris-HCl-buffer What was dissolved.

<(E) component>
The composition of the present invention contains, as the component (e), a nonionic compound having 20 to 500 mol of alkylene oxide in the molecule.

  Examples of the component (e) include polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl ether, alkyl glycoside, polyoxyalkylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyalkylene glycol, and the like. No. Among these, a nonionic compound represented by the general formula (1) is preferable from the viewpoint of efficiently generating an organic peracid.

Y- (R ⁷ -O) _m -R ⁸ (1)
Wherein, Y represents hydrogen or ^R 9 -O-, ^{R 9} and ^{R 8} individually represents hydrogen, alkyl or alkenyl group having 2 to 20 carbon atoms having 1 to 20 carbon atoms, ^{R 7} carbon It shows the alkylene group of number 2-6, and m shows the integer of 20-500. Y and R ⁸ do not simultaneously become hydrogen. ]
As the nonionic compound represented by the general formula (1), polyoxyalkylene (preferably ethylene oxide and / or propylene oxide, preferably having an addition mole number of 20 to 50, and more preferably having an addition mole number of 22 to 35) alkyl ( (C8-C20 is preferable, C10-C18 is more preferable, C10-C14 is more preferable.) Ether is preferable.

  The content of the component (e) in the composition of the present invention is 1 to 30% by mass, and 2 to 25% by mass in terms of efficiently generating an organic peracid by synergistic action with the component (d). Is preferably 2 to 20% by mass, and more preferably 2 to 10% by mass. The ratio of the component (d) to the component (e) [the amount of the component (d) per 1 g of the component (e)] is preferably 1 to 1000 KLU / g, more preferably 10 to 500 KLU / g, and more preferably 20 to 300 KLU / g. More preferred.

  In addition, the component (d) and the component (e) are components that efficiently generate an organic peracid by a synergistic action and improve the bleaching power. Therefore, by utilizing such an action, in the aqueous washing using the bleaching detergent containing the components (a), (b) and (c), the components (d) and (e) are bleached. The present invention can also be applied to a cleaning method used as an enhancer.

  When applied as such a washing method, the component (a) is 0.0001 to 0.01% by mass (preferably 0.0005 to 0.05% by mass), and the component (b) is 0.0001 to 0%. Aqueous detergent containing 0.005% by mass (preferably 0.0001 to 0.003% by mass) and 0.0005 to 0.02% by mass (preferably 0.0015 to 0.02% by mass) of component (c) In the system, component (d) is 0.1 to 700 KLU / 100 ml (preferably 0.2 to 700 KLU / 100 ml), and component (e) is 0.0005 to 0.02% by mass (preferably 0.001 to 0. 02% by mass).

<Other components>
Examples of the surfactant other than the component (c) include an anionic surfactant, an amphoteric surfactant, and a cationic surfactant.

  Examples of anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylated sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts and esters thereof. Salts or fatty acid salts. In particular, a linear alkylbenzene sulfonate having an alkyl chain having 10 to 18 (preferably 12 to 14) carbon atoms and an α-sulfofatty acid alkyl ester salt having 10 to 20 carbon atoms are preferable. Examples of the counter ion include alkali metals, alkaline earth metals, ammonium, and alkanolamines. From the viewpoint of adjusting the dissolution rate, it is also preferable to use potassium ions in combination. The potassium ion in all the counter ions is preferably 5% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more.

  Examples of the cationic surfactant include an alkyltrimethylammonium salt and the like, and examples of the amphoteric surfactant include a carbobetaine-type and a sulfobetaine-type amphoteric surfactant.

  Among the above-mentioned surfactants, in terms of cleaning performance and solubility, the amount corresponding to the surfactant described in JIS K3362: 1998 is preferably 10 to 60% by mass, more preferably 15 to 45% by mass, and 18 to 40% by mass. % Is more preferable, and 20 to 35% by mass is particularly preferable.

  The composition of the present invention comprises a builder, another bleaching activator, a re-staining inhibitor (such as carboxymethylcellulose), a softener (such as a dialkyl-type quaternary ammonium salt, or a clay mineral), and a reducing agent (such as a sulfite). And additives such as a fluorescent whitening agent (biphenyl type, aminostilbene type, etc.), a foam control agent (silicone, etc.), a fragrance, and an enzyme (protease, pectinase, amylase, lipase, etc.).

  In the present invention, the builder itself has no detergency by itself, or is not so remarkable, but when added to the composition, remarkably improves the detergency, and a polyvalent metal cation-trapping action, At least one of the three functions of the soil dispersing action and the alkaline buffering action is performed. Examples of the builder include a water-soluble inorganic compound, a water-insoluble inorganic compound, and an organic compound.

  Examples of the water-soluble inorganic compound include phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, sulfates and the like. Of these, phosphates are preferred in that they perform all three functions.

  Examples of the water-insoluble inorganic compound include aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, amorphous aluminosilicate and the like), crystalline silicate and the like. Among these, A-type zeolite having a particle diameter of 3 μm or less (more preferably 1 μm or less) is preferable.

  Examples of the organic compound include carboxylate (aminocarboxylate, hydroxyaminocarboxylate, hydroxycarboxylate, cyclocarboxylate, maleic acid derivative, oxalate, etc.) and organic carboxylic acid (salt) polymer (acrylic acid) Polymers and copolymers, polyvalent carboxylic acid polymers and copolymers, glyoxylic acid polymers, polysaccharides and salts thereof). Among these, an organic carboxylic acid (salt) polymer is preferable.

  In the builder salt, the counter ion is preferably an alkali metal salt or an amine, particularly preferably sodium and / or potassium, monoethanolamine or diethanolamine.

  In the composition of the present invention, the builders can be used alone or in combination of two or more. In particular, the builder preferably contains the water-soluble inorganic compound, more preferably uses a water-soluble inorganic compound and an organic compound in combination, and uses a water-soluble inorganic compound, an organic compound and a water-insoluble inorganic compound in combination. More preferred.

  In the composition of the present invention, the total content of the builder in the composition is preferably from 20 to 80% by mass, more preferably from 30 to 70% by mass, and still more preferably from 35 to 60% by mass, from the viewpoint of cleaning performance. Further, the content of the water-soluble inorganic compound builder in the composition is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass. The content of the water-insoluble inorganic compound builder in the composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass. The organic compound builder in the composition is preferably 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and still more preferably 0.5 to 10% by mass.

  The composition of the present invention preferably contains a builder having a polyvalent metal cation-trapping action, particularly from the viewpoint of cleaning performance. As a builder having a polyvalent metal cation-trapping action, it is preferable to contain a compound having a calcium stability constant of 4 to 15 (preferably 5 to 14, more preferably 6 to 13). The content of the builder capable of capturing polyvalent metal cations in the composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass. In the present invention, the calcium stability constant is determined by the following method.

(Method of measuring calcium stability constant)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10) solution is prepared as a buffer. All sample solutions are prepared using this buffer. For the measurement of the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, the relationship between the calcium chloride concentration and the potential of the electrode is determined, and a calibration curve is created. 5.36 × ¹⁰ -2 mol / l solution of calcium chloride, a 5.36 × ¹⁰ -4 mol / l solution of a chelating agent sample are prepared. 1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the mixture is stirred for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The calcium stability constant (Ca stability constant) is determined from the following equation, assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1.

  As other bleach activators, glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, and compounds described in the following general formulas (2) and (3), etc. Can be contained.

[Wherein, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , and R ¹⁷ are each independently an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group, and R ¹⁵ is 2 to 10 alkylene groups, and X ⁻ represents an anion. ]
<Bleaching detergent composition>
The composition of the present invention preferably has a pH of 0.1 to 12% by mass, as measured at 20 ° C. described in JIS K3362: 1998, of 8 to 12, and 9 to 11.5 in terms of cleaning performance and damageability. More preferably, it is more preferably from 9.5 to 11, and particularly preferably from 10 to 11. The pH is preferably adjusted with a pH adjuster, such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal silicates such as sodium silicate and potassium silicate. Salts and the like can be used.

  From the viewpoint of solubility, the composition of the present invention preferably has an apparent density of 1600 g / L or less, more preferably 1300 g / L or less, as measured by the method defined by JIS K 3362: 1998, More preferably, it is 1000 g / L or less. Further, in terms of convenience and reduction of waste (eg, boxes and the like), the apparent density is preferably 300 g / L or more, more preferably 600 g / L or more, and further preferably 700 g / L or more. preferable.

  In terms of solubility, the composition of the present invention has a mean particle size of 150 to 1000 μm obtained by vibrating for 5 minutes using a standard sieve of JIS Z 8801, and then calculating from the mass fraction according to the sieve size. It is preferably 150 to 800 μm, more preferably 180 to 600 μm.

  For convenience, the composition of the present invention may be further compressed into a tablet form, or a single use amount may be stored in a water-soluble or water-insoluble container.

  The composition of the present invention is preferably formed into particles and then subjected to surface modification with a surface coating agent in terms of fluidity and non-caking properties. The surface coating agent is preferably 1 to 30% by mass, more preferably 2 to 15% by mass, and still more preferably 5 to 10% by mass in the detergent particles.

  Examples of the surface coating agent include silicate compounds such as aluminosilicate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds, metal soaps, powdered surfactants, and the like. Water-soluble polymers such as fine powder, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof, and fatty acids. Of these, water-insoluble inorganic substances are preferred, and crystalline aluminosilicates, amorphous aluminosilicates, and crystalline silicate compounds are particularly preferred.

Example 1
A slurry having a solid content of 48% by mass is spray-dried at a hot air temperature of 250 ° C., and based on a powder detergent composition, 4% by mass of sodium polyacrylate (average molecular weight 10,000), 16% by mass of sodium carbonate, 16% by mass of sodium sulfate Thus, base granules of 0.1% by mass of fluorescent dye, 16% by mass of zeolite and 0.5% by mass of water were obtained.

  Next, the base granules are charged into a Ladyge mixer (manufactured by Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and polyoxyethylene alkyl ether (carbon number of alkyl group: 12 to 14) is stirred under a main shaft (150 rpm). EO average addition mole number) 7% by mass, Brij 35 (polyoxyethylene alkyl ether having an alkyl group carbon number of 12 and EO average addition number of 23) 2% by mass, linear alkyl (C10 to C13) benzene A mixed solution of 10% by mass of sodium sulfonate, 2% by mass of soap, 1% by mass of PEG, and 2% by mass of water was charged over 3 minutes, and then stirred for 5 minutes.

  Further, 8% by mass of crystalline silicate and 10% by mass of zeolite were added to the mixer to coat the surface. After passing through a 2000 μm sieve, transfer to a ribbon mixer, add sodium percarbonate, peracid precursor, lipase granulation (Lipolase 100T), protease granulation (cannase 24TK), and flavor, mix and mix Was obtained.

Examples 2 to 4, Comparative Examples 1 to 8
In the same manner as in Example 1, powder bleaching detergent compositions shown in Table 1 were obtained.

<Bleaching effect>
Add the powder composition shown in Table 1 at 0.067% by mass, at 20 ° C., 1 liter, and add 5 pieces of curry-stained cloth (lipophilic stain) prepared as described below. After washing (80 rpm × 10 minutes), the sample was rinsed with tap water, dried, and the bleaching ratio was calculated by the following equation. The reflectance was measured using ND-300A manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

Bleaching washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectivity of original cloth−reflectance before washing)] × 100
<Preparation of curry-contaminated cloth>
After the solid content of the house food retort curry (curry Marche) was removed with a mesh, the obtained liquid was heated to boiling. Cotton gold cloth # 2003 was dipped in this solution and boiled for about 15 minutes. The mixture was removed from the heat and left for about 2 hours, and then the cloth was taken out. The excess curry liquid was removed with a spatula and air-dried. Then, it pressed and used for the experiment as a 10 cm x 10 cm test piece.

-Na percarbonate: sodium carbonate hydrogen peroxide adduct, sodium percarbonate; bleach particles described in paragraph 0019 of JP-A-2000-256699)
LOBS: sodium lauroyloxybenzenesulfonate granules (bleach particles described in paragraph 0018 of JP-A-2000-256699)
DOBA: (decanoyloxybenzoic acid granulated product; prepared by the same method as the method for producing bleach particles described in paragraph 0018 of JP-A-2000-256699, replacing LOBS with DOBA)
-AE: polyoxyethylene alkyl ether having 12 to 14 carbon atoms in the alkyl group and an average number of moles of added EO of 7-Lipase: Lipolase 100T (manufactured by Novo) (100 KLU / g)
Brij35 (a polyoxyethylene alkyl ether having an alkyl group having 12 carbon atoms and an EO average addition mole number of 23, manufactured by Wako Pure Chemical Industries, Ltd.)
-PEG: polyethylene glycol (average molecular weight 8500)
・ Protease: Cannase 24TK (Novo)
-Crystalline silicate: Powder SKS-6 (manufactured by Hoechst Tokuyama Corporation)
-Sodium polyacrylate: sodium polyacrylate (average molecular weight 10,000)
・ Fluorescent agent: Tinopearl CBS-X (manufactured by Ciba Geigy)
As is clear from the table, Comparative Examples 2 to 4 and Comparative Example 8 contain the components (a) to (c) but do not contain any one of the components (d) and (e). However, the bleaching ratio was inferior to the examples. Particularly, from the comparison between Example 1 and Comparative Example 3 and the comparison between Examples 3 and 4 and Comparative Example 4, the components (d) and (e) are used together with the components (a) to (c). As a result, it was confirmed that the bleaching and washing effect was greatly enhanced.

Claims (6)

(A) 0.1 to 20% by mass of a peroxide that generates hydrogen peroxide in an aqueous solution, and (b) a peroxide represented by the following general formula (I) that reacts with hydrogen peroxide to generate an organic peracid. 0.05 to 10% by mass of an acid precursor, (c) 1 to 30% by mass of a nonionic surfactant having 0 to 15 mol of alkylene oxide in a molecule, (d) an enzyme having lipase and / or esterase activity, and (E) A bleaching detergent composition containing 1 to 30% by mass of a nonionic compound having 20 to 500 mol of alkylene oxide in a molecule.

[Wherein, R ₁ is a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group having 4 to 18 carbon atoms, an acyl group having 4 to 18 carbon atoms, or a compound represented by the following general formula (II) ) Represents a group represented by

(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group, alkenyl group or acyl group having 1 to 18 carbon atoms;
R ₃ represents a linear or branched alkylene group having 1 to 8 carbon atoms;
p represents 0 or 1;
R ₄ represents a phenylene group which may be substituted with a linear or branched alkylene group having 1 to 8 carbon atoms or a linear or branched alkyl group having 1 to 5 carbon atoms;
A represents a linear or branched alkylene group having 1 to 4 carbon atoms;
q is an average number of added moles of alkylene oxide, and represents a number of 0 to 100, and q A's may be the same or different)
L represents a group represented by the following general formula (III), (IV), (V), or (VI).

(Wherein, M represents a hydrogen atom or a cation forming a water-soluble salt, and R ₅ and R ₆ represent a linear or branched alkylene group having 1 to 8 carbon atoms)]   The bleaching detergent composition according to claim 1, wherein the component (a) is an adduct of sodium carbonate and hydrogen peroxide. The component (b) is represented by the formula (I) wherein R ¹ is a linear or branched alkyl group having 4 to 18 carbon atoms, an aryl group, an alkenyl group having 4 to 18 carbon atoms, and an acyl having 4 to 18 carbon atoms. The bleaching detergent composition according to claim 1 or 2, wherein the group, L, is a group represented by formulas (III), (IV).   The bleaching detergent composition according to any one of claims 1 to 3, wherein the component (c) is a polyoxyalkylene alkyl ether obtained by adding 4 to 15 mol of ethylene oxide and / or propylene oxide to an alcohol having 10 to 18 carbon atoms. . The bleaching detergent composition according to any one of claims 1 to 4, wherein the component (e) is a nonionic compound represented by the general formula (1).
Y- (R ⁷ -O) _m -R ⁸ (1)
Wherein, Y represents hydrogen or ^R 9 -O-, ^{R 9} and ^{R 8} individually represents hydrogen, alkyl or alkenyl group having 2 to 20 carbon atoms having 1 to 20 carbon atoms, ^{R 7} carbon It shows the alkylene group of number 2-6, and m shows the integer of 20-500. Y and R ⁸ do not simultaneously become hydrogen. ] (A) a peroxide that generates hydrogen peroxide in an aqueous solution, (b) a peracid precursor represented by the above general formula (I) that reacts with hydrogen peroxide to generate an organic peracid, (c) In an aqueous washing using a bleaching detergent containing a nonionic surfactant having 0 to 15 moles of alkylene oxide in the molecule, (d) an enzyme having lipase and / or esterase activity, and (e) an alkylene in the molecule. A washing method using a nonionic compound having 20 to 500 moles of an oxide as a bleaching agent.