JP4188222B2 - Bleach cleaning composition - Google Patents

Description

  The present invention relates to a bleaching detergent composition suitable for textiles, a washing method, and the like.

  Detergent compositions are strongly directed toward higher density and lower usage due to consumer convenience and consideration for the environment. In addition, there is a trend toward saving water, low-temperature washing, and shortening of washing time due to consumer needs such as “I want to finish washing easily” and “I want to wash clothes carefully”, environment, energy and economy. is there.

  Dirt that adheres to clothing, etc. in daily life has also diversified due to changes in the living environment. Washing with ordinary detergent alone against so-called stain stains such as blood stains, food stains, plant pigment stains, and lipophilic stains The cleaning power is not enough. In particular, wrinkles and cuff stains cannot be completely removed by ordinary washing, and such residual sebum causes yellowing of clothing during storage.

  Since a bleaching agent is very effective for these stains and the like, a bleaching component is blended in a detergent. The bleaching component is roughly divided into oxygen and chlorine. Examples of the chlorine-based ones include hypochlorous acid and dichlorocyanuric acid. These have problems in stability, odor, etc., and are not suitable for detergent blending, and because of their strong bleaching power, they have to be nervous about the use in clothing color and pattern. Oxygen bleach has a slightly lower bleaching power at room temperature than chlorine bleach, but it does not lose color even when applied to colored or patterned clothing, and the fabric may not be damaged and yellowing may occur. It is widely used as a cleaning agent because it does not exist. In addition, in order to improve the bleaching performance, an organic peracid precursor or the like is also used in combination.

  The nonionic surfactant used as a detergent base has good hard water resistance, outstanding detergency of oily dirt such as sebum dirt, and very good biodegradability. The technical development of a detergent containing a nonionic surfactant has been actively conducted.

  However, in a bleaching system that uses a combination of a detergent containing a nonionic surfactant and an organic peracid precursor, the organic peracid precursor has a high affinity with the nonionic surfactant and is not contained in the micelle of the nonionic surfactant. Since it is taken in strongly and it is difficult to get out of the micelle, the amount of peracid generated is reduced, and the bleaching power is greatly reduced. For this reason, studies have been made to improve the bleaching detergency of detergents containing nonionic surfactants and organic peracid precursors. For example, improvement in bleaching power by containing a metal ion sequestering agent is known (see, for example, Patent Documents 1, 2, and 3). However, these techniques reduce the bleaching power by sequestering metal ions in the washing bath. It is to prevent.

In addition, it is known to use an alkylene terephthalate unit and / or a polymer compound having an alkylene isophthalate unit and a polyoxyalkylene unit as one component of a cleaning composition. Only addition to a cleaning agent is being studied as an improving agent and a soil removing agent. (For example, refer to Patent Documents 4, 5, 6, 7, and 8.) It has been known that the cleaning power is improved by the anti-recontamination effect and the dirt removal effect, but the generated organic peracid is efficiently used. The effect of enhancing the bleaching detergency by bringing it into contact with the object to be cleaned has not been known.
JP-A-9-3497 JP-A-10-316996 Japanese Patent Laid-Open No. 11-35978 JP 2002-167596 A JP 2002-194391 A JP 10-298597 A Japanese National Patent Publication No. 11-512136 Special Table 2002-520477

  The subject of this invention is providing the bleaching detergent composition which shows the outstanding cleaning performance with respect to yellowing stain | pollution | contamination, such as a sebum stain and underwear, a washing | cleaning method, etc.

  In the course of research on improving the bleaching detergency of a detergent containing a nonionic surfactant and an organic peracid precursor, the present inventor has found that a high amount of alkylene terephthalate units and / or alkylene isophthalate units and polyoxyalkylene units is used. It has been found that when a molecular compound is used in combination, the produced organic peracid can be efficiently brought into contact with an object to be cleaned, and the bleaching detergency can be enhanced, thereby completing the present invention.

  That is, the present invention provides, as a means for solving the above problems, (a) a peroxide that generates hydrogen peroxide in an aqueous solution, (b) a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid, A bleaching detergent composition containing a nonionic surfactant and (d) an alkylene terephthalate unit and / or a polymer compound having an alkylene isophthalate unit and a polyoxyalkylene unit, a washing method, and the like. is there.

  The composition of the present invention is obtained by blending the combined system of the components (a) to (c) with a polymer compound having an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene unit as the component (d). Because of the action of the polymer compound, the generated organic peracid comes into contact with the object to be cleaned efficiently, so that the bleaching detergency is enhanced.

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

  As component (a), carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / hydrogen peroxide adduct, urea / hydrogen peroxide Examples include adducts. Among these, carbonate / hydrogen peroxide adduct and 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 or an organic compound 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, polyvinyl pyrrolidone, and hydroxypropyl cellulose.

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

  In the case of using a component coated with an inorganic or organic compound as the component (a), it can be produced by applying the method described in, for example, JP-A No. 59-196399.

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

<(B) component>
The composition of this invention contains the peracid precursor which reacts with hydrogen peroxide and produces | generates an organic peracid as (b) component.

  (B) As a peracid precursor of a component, what is represented by following formula (I) is preferable.

[Wherein, R ₁ represents 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 the following general formula (II )

(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, or an acyl group;
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 the average number of moles of alkylene oxide added and represents a number from 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).

(In the formula, 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)]
R ₁ in the general formula (I) is a linear or branched alkyl group or alkenyl having 4 to 18 carbon atoms, preferably 7 to 18 carbon atoms, more preferably 10 to 13 carbon atoms, from the viewpoint of cleaning performance. A group (more preferably an alkyl group).

  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 is preferably a cation that forms a water-soluble salt, and examples thereof include alkali metal ions, alkaline earth metal ions, ammonium salts, alkanolamine salts, etc. Among them, sodium ions and potassium ions are preferable, and sodium is particularly preferable. Ions are preferred.

  Further, as the peracid precursor of the component (b), glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, and the following general formulas (1), (2 ) And the like can be used.

[Wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ are each independently an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, and R ¹² is a carbon number 2 to 10 alkylene groups, and X ⁻ represents an anion. ]
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 the 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 the washing bath, the particles containing the component (b) are at least one selected from polyoxyalkylene alkyl ethers, alkyl sulfates and polyoxyalkylene alkyl ether sulfates. The surfactant is preferably 50% by mass or less, more preferably 1 to 45% by mass, and still more preferably 2 to 40% by mass.

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

  The alkyl sulfate has 10 to 18 carbon atoms and is preferably a sodium salt, particularly sodium lauryl sulfate or sodium myristyl sulfate.

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

  (B) The particle | grains containing a component may mix | blend the binder chosen from a polyoxyethylene and a fatty acid as a component for making formulation easy.

  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 having 8 to 20 carbon atoms, more preferably 10 to 18 carbon atoms, and particularly 12 to 18 carbon atoms are preferred, and these may be in the form of sodium or potassium soap. The binder is preferably used in the particle containing the component (b) in an amount of 0.5 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 5 to 20% by mass.

  For the purpose of improving the stability of the particles containing the component (b), an acidic substance may be further blended with the composition of the present invention as desired.

  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 blending 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 with an ordinary granulator. In particular, the surface activity for improving solubility with the component (b) A method in which part or all of the agent is first mixed and then a binder or the like is added is preferable. The binder is preferably added after being melted in advance at 40 to 100 ° C., further 50 to 100 ° C., particularly 50 to 90 ° C.

  The granulation method is preferably an extrusion granulation method, and a granulated product having an average particle diameter of 500 μm to 5000 μm, particularly 500 to 3000 μm is preferable. In addition, it is possible to apply a tablet shape by a briquetting machine as a preferable granulation method.

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

<(C) component>
The composition of the present invention contains a nonionic surfactant as component (c). As the nonionic surfactant of component (c), polyoxyalkylene alkyl (carbon number 8 to 20) ether, alkyl polyglycoside, polyoxyalkylene alkyl (carbon number 8 to 20) phenyl ether, polyoxyalkylene sorbitan fatty acid ( Examples include esters having 8 to 22 carbon atoms, polyoxyalkylene glycol fatty acid (8 to 22 carbon atoms) esters, and polyoxyethylene polyoxypropylene block polymers. In particular, from the viewpoint of cleaning performance, the component (c) is preferably a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 20 moles of an alkylene oxide such as ethylene oxide or propylene oxide to an alcohol having 10 to 18 carbon atoms. The component (c) preferably has an HLB value (calculated by the Griffin method) of 10.5 to 15.0, more preferably 11.0 to 14.5 in terms of cleaning performance.

  In the composition of the present invention, the component (c) (contains 10% by mass or more when the surfactant equivalent by the measurement method described in JIS K3362: 1998 is 100% by mass) is preferably 10% by mass or more. 30 mass% or more is more preferable, and 50 mass% or more is still more preferable. In addition, it is preferable to use an anionic surfactant together with the nonionic surfactant in terms of cleaning performance against various types of dirt, and the mass ratio of the nonionic surfactant 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.

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

<(D) component>
The composition of the present invention contains a polymer compound having an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene unit as the component (d). The component (d) is easily adsorbed to the surface of the fiber that is the object to be cleaned or the dirt surface to which the oil component (sebum component) is adhered via hydrophobic interaction. It is a component that expresses the role of a binder between acids and acts to improve bleach detergency.

  The component (d) is a polymer compound polymerized randomly or in blocks with an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene terephthalate unit as basic units. In addition, in order to improve the dispersibility in water, a polymer compound into which a part of sulfonic acid group is introduced can be used.

  As an alkylene terephthalate unit, 1 or 2 or more chosen from an ethylene terephthalate unit, a propylene terephthalate unit, a butylene terephthalate unit, etc. are mentioned, Among these, an ethylene terephthalate unit is preferable.

  Examples of the alkylene isophthalate unit include one or more selected from an ethylene isophthalate unit, a propylene isophthalate unit, a butylene isophthalate unit, and the like. Among these, an ethylene isophthalate unit is preferable.

  Examples of the polyoxyalkylene unit include one or more selected from a polyoxyethylene unit, a polyoxypropylene unit, a polyoxyethylene polyoxypropylene unit, and the like.

  The molar ratio of the alkylene terephthalate unit and / or the alkylene isophthalate unit and the polyoxyalkylene unit is preferably 90/10 to 40/60, more preferably 80/20 to 45/55, from the viewpoint of improving the bleaching performance. 30-50 / 50 is more preferable.

  The weight average molecular weight of the component (d) is preferably 6000 to 85000 in terms of bleaching performance.

  The content of the component (d) in the composition of the present invention is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and still more preferably 2 to 10% by mass in terms of cleaning performance. 5% by mass is particularly preferred. By blending the component (c) and the component (d) at a specific ratio, the organic peracid generated from the component (a) and the component (b) can be effectively released out of the micelle and adsorbed on the clothing. it can. From the above viewpoint, the ratio of the component (c) to the component (d) is preferably (d) / (c) = 0.25 to 5.0, more preferably 0.5 to 3.0 in terms of mass ratio. 0.8 to 2.5 is more preferable.

Further, since the component (d) can improve the bleaching detergency even when added later to the aqueous detergent system containing the components (a), (b) and (c), d) It can also be applied as a cleaning method using the action of the component. In addition, when applying as a washing | cleaning method, (a) Component 5.0 * 10 < ^-5 > -0.02 mass% (preferably 0.001-0.01 mass%), (b) Component 2.0 * 10 ^{−5 to} 0.01 mass% (preferably 5.0 × 10 ^{−4 to} 0.005 mass%), (c) 0.001 to 0.02 mass% (preferably 0.005 to 0.02) (D) component 1.5 to 200 parts by mass, preferably 1.5 to 150 parts by mass with respect to 100 parts by mass of the total amount of components (a) to (c). It is desirable to add parts by weight.

  Further, as described above, the component (d) is a component that acts to improve bleach cleaning properties, so that (a) a peroxide that generates hydrogen peroxide in an aqueous solution, (b) hydrogen peroxide and It can be used as a bleach improver in aqueous cleaning using a peracid precursor that reacts to produce an organic peracid and (c) a bleach cleaner containing a nonionic surfactant. When the component (d) is used as a bleaching improver, the amount added can be the same as that in the washing method described above.

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

  Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or esters thereof. A salt or a fatty acid salt is mentioned. In particular, linear alkylbenzene sulfonates having 10 to 18 (preferably 12 to 14) carbon atoms in the alkyl chain and α-sulfo fatty acid alkyl ester salts having 10 to 20 carbon atoms are preferred. Examples of the counter ion include alkali metals, alkaline earth metals, ammonium, and alkanolamine. From the viewpoint of adjusting the dissolution rate, it is also preferable to use potassium ions in combination. The potassium ion in all 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 alkyltrimethylammonium salts, and examples of the amphoteric surfactant include carbobetaine type and sulfobetaine type amphoteric surfactants.

  Among the surfactants described above, the surfactant equivalent by the measuring method described in JIS K3362: 1998 is preferably 10 to 60% by mass, more preferably 15 to 45% by mass, in terms of cleaning performance and solubility. -40 mass% is still more preferable, and 20-35 mass% is especially preferable.

  The composition of the present invention comprises a builder, other bleach activators, anti-staining agents (such as carboxymethyl cellulose), softeners (such as dialkyl quaternary ammonium salts and clay minerals), and reducing agents (such as sulfites). Additives such as fluorescent whitening agents (biphenyl type, aminostilbene type, etc.), foam control agents (silicone, etc.), perfumes, enzymes (proteases, pectinases, amylases, lipases, etc.) can be added.

  In the present invention, the builder itself does not have a detergency itself or is not so remarkably present, but when it is added to the composition, it significantly improves the detergency, At least one of the three functions of the soil dispersing action and the alkali buffering action is performed. Examples of the builder include water-soluble inorganic compounds, water-insoluble inorganic compounds, and organic compounds.

  Examples of the water-soluble inorganic compound include phosphates (tripolyphosphate, pyrophosphate, metaphosphate, trisodium phosphate, etc.), silicates, carbonates, sulfates, and the like. Among these, phosphate is preferable in that it performs all three functions.

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

  Organic compounds include carboxylates (aminocarboxylates, hydroxyaminocarboxylates, hydroxycarboxylates, cyclocarboxylates, maleic acid derivatives, oxalates, etc.), organic carboxylic acid (salt) polymers (acrylic acid) Polymer and copolymer, polyvalent carboxylic acid polymer and copolymer, glyoxylic acid polymer, polysaccharides and salts thereof, and the like. Among these, organic carboxylic acid (salt) polymers are preferable.

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

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

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

  In the composition of the present invention, it is preferable to contain a builder having a scavenging action for polyvalent metal cations, particularly in terms of cleaning performance. 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) as a builder capable of capturing a polyvalent metal cation. 0.1-20 mass% is preferable, as for content in the builder composition which has the capture | acquisition action of a polyvalent metal cation, 0.5-15 mass% is more preferable, and 1-10 mass% is still more preferable. In the present invention, the calcium stability constant is determined by the following method.

(Measurement method of calcium stability constant)
_{0.1mol / NH 4 Cl-NH 4} OH (pH10) liters to prepare a solution as a buffer. All sample solutions are prepared using this buffer. For measuring the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, a relationship between the calcium chloride concentration and the electrode potential is obtained, 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. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. Assuming that the chelating agent forms a chelate complex with Ca ²⁺ at 1: 1, the calcium stability constant (Ca stability constant) is obtained from the following formula.

<Bleaching detergent composition>
The composition of the present invention preferably has a pH of 0.1 to 12 mass% measured at 20 ° C. described in JIS K3362: 1998, in terms of cleaning performance and damage, and is 9 to 11.5. More preferably, it is more preferably 9.5 to 11, and particularly preferably 10 to 11. The pH is preferably adjusted with a pH adjusting agent, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal silicates such as sodium silicate and potassium silicate. A salt or the like can be used.

  In terms 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 a method defined by JIS K 3362: 1998. More preferably, it is 1000 g / L or less. In terms of convenience and reduction of waste (such as boxes), the apparent density is preferably 300 g / L or more, more preferably 600 g / L or more, and more 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 determined from the mass fraction according to the size of the sieve mesh after being vibrated for 5 minutes using a standard sieve of JIS Z 8801. Is preferable, more preferably 150 to 800 μm, still more preferably 180 to 600 μm.

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

  In terms of fluidity and non-caking property, the composition of the present invention is preferably made into a particle form and then subjected to surface modification with a surface coating agent. 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 aluminosilicates, calcium silicates, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate compounds such as silicate compounds, metal soaps, powder surfactants, etc. Water-soluble polymers such as fine powders, carboxymethylcellulose, polyethylene glycol, sodium polyacrylate, polycarboxylic acid salts such as copolymers of acrylic acid and maleic acid or salts thereof; and fatty acids. Among these, water-insoluble inorganic substances are preferable, and crystalline aluminosilicates, amorphous aluminosilicates, and crystalline silicate compounds are particularly preferable.

Example 1
A slurry with 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, sodium polyacrylate (average molecular weight 10,000) 4% by mass, sodium carbonate 16% by mass, sodium sulfate 16% by mass Base granules of 0.1% by weight of fluorescent dye, 16% by weight of zeolite and 0.5% by weight of water were obtained.

  Next, the base granule was put into a Redige mixer (Matsusaka Giken Co., Ltd., capacity 20L, with jacket), 7% by mass of nonionic surfactant, straight chain alkyl (carbon number) with stirring of the main shaft (150rpm) 10 to 13) A mixed solution of 10% by mass of sodium benzenesulfonate, 2% by mass of soap, 1% by mass of PEG, and 2% by mass of water was added in 3 minutes, and then stirred for 5 minutes.

  Further, 8% by mass of crystalline silicate and 10% by mass of zeolite were charged into this mixer to perform surface coating. After passing through a 2000 μm sieve, it was transferred to a ribbon mixer, and sodium percarbonate, peracid precursor, polyoxyethylene terephthalate particles, enzyme, and fragrance were added and mixed to obtain a powder bleach detergent composition.

Examples 2-4, Comparative Examples 1-5
In the same manner as in Example 1, the powder bleach detergent composition shown in Table 1 was obtained.

<Bleaching effect>
Add the powder detergent shown in Table 1 to 0.067 mass%, 20 ° C, 1 liter, add 5 sheets of curry-stained cloth (lipophilic soil) prepared as follows, and use a targotometer After washing (80 rpm × 10 minutes), it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. The reflectance was measured with ND-300A manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter.

Bleach washing rate (%) = [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)] × 100
<Preparation of curry-contaminated cloth>
After removing the solid content of the house food retort curry (curry marche) with a mesh, the resulting liquid was heated until boiling. Cotton gold cloth # 2003 was immersed in this solution and boiled for about 15 minutes. After removing from the fire as it was and leaving it to stand for about 2 hours, the cloth was taken out and the curry liquid adhering to the excess was removed with a spatula and allowed to dry naturally. Thereafter, it was pressed and subjected to an experiment as a 10 cm × 10 cm test piece.

Na percarbonate: sodium carbonate hydrogen peroxide adduct, sodium percarbonate; bleaching agent particles described in paragraph 0019 of JP-A No. 2000-256699)
LOBS: sodium lauroyloxybenzenesulfonate granulated product (bleaching agent particles described in paragraph 0018 of JP 2000-256699 A)
DOBA: Decanoyloxybenzoic acid granulated product (prepared by replacing LOBS with DOBA in the same production method as the bleaching particle described in paragraph 0018 of JP-A-2000-256699)
AE: polyoxyethylene alkyl ether having 12 to 14 carbon atoms in the alkyl group and an EO average addition mole number of 7 POET: polyoxyethylene terephthalate (Repel-O-Tex-SRP4 manufactured by Rhodia)
PEG: polyethylene glycol (average molecular weight 8500)
Enzyme: Cellulase K (described in JP-A-63-264699), cannase 24TK (manufactured by Novo) at a weight ratio of 3: 1 Crystalline silicate: powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.)
-Polyacrylic acid Na: sodium polyacrylate (average molecular weight 10,000)
・ Fluorescent agent: Chino Pearl CBS-X (Ciba Geigy)
As is clear from the results of the table, the compositions of Comparative Examples 2 and 3 do not contain the component (d), so the contact between the produced organic peracid and the object to be cleaned (curry contaminated cloth) is an example. As a result, the bleaching washing rate is considered to have decreased.

Claims (4)

  (A) a peroxide that generates hydrogen peroxide in an aqueous solution, (b) a peracid precursor that reacts with hydrogen peroxide to produce an organic peracid, (c) a nonionic surfactant, and (d) 2 to 20% by mass of a polymer compound having an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene unit, and the ratio of the component (c) to the component (d) is (d) component / ( c) Bleach detergent composition where component = 0.5-5.0.   (A) 0.1 to 20% by mass of a peroxide that generates hydrogen peroxide in an aqueous solution, (b) 0.05 to 10% by mass of a peracid precursor that reacts with hydrogen peroxide to generate an organic peracid. (C) Nonionic surfactant (contains 10% by mass or more in the case where the surfactant equivalent according to the measurement method described in JIS K3362: 1998 is 100% by mass) 1-30% by mass, and (d 2. The bleaching detergent composition according to claim 1, comprising 2 to 20% by mass of a polymer compound having an alkylene terephthalate unit and / or an alkylene isophthalate unit and a polyoxyalkylene unit. The bleaching detergent composition according to claim 1 or 2, wherein the component (b) is represented by the following general formula (I).

[Wherein, R ₁ represents 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 the following general formula (II )

(Where
R ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, or an acyl group;
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 the average number of moles of alkylene oxide added and represents a number from 0 to 100, and q A's may be the same or different.
L represents a group represented by the following general formula (III).

(In the formula, 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 component (d) is a polymer compound having a molar ratio of alkylene terephthalate and / or alkylene isophthalate units to polyoxyalkylene units of 90/10 to 40/60 and a weight average molecular weight of 6000 to 85,000. The bleach detergent composition according to any one of -3.