JP4188221B2 - Bleach cleaning composition - Google Patents

Description

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

  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, it is known that bleaching power is improved by containing a sequestering agent (see, for example, Patent Documents 1, 2, and 3), but an organic peracid precursor is incorporated into a micelle of a nonionic surfactant. However, this does not solve the phenomenon that the bleaching power decreases.

In addition, it is known that cyclodextrin is used as a component of a cleaning composition, but conventionally, for suppressing skin irritation (see, for example, Patent Document 4), from a dyed fiber product to another fiber product. In order to suppress the migration of the dye (for example, see Patent Document 5), and for the deodorizing effect (for example, see Patent Documents 6, 7, and 8), these are only included.
JP-A-9-3497 JP-A-10-316996 Japanese Patent Laid-Open No. 11-35978 JP-A-3-17297 JP-T-2001-523310 JP 2000-290690 A JP 2000-290700 A JP 2002-88396 A

  The subject of this invention is providing the manufacturing method suitable as a manufacturing method of the bleaching detergent composition excellent in especially the bleaching detergency of textiles, and the said bleaching detergent composition. More specifically, a bleaching detergent composition having enhanced bleaching detergency by efficiently increasing the amount of peracid generated from the organic peracid precursor, a production method suitable as a method for producing the bleaching detergent composition, and It is to provide a cleaning method.

  The present invention provides, as means for solving the problems, (a) one or more compounds selected from surfactants, (b) one or more compounds selected from compounds that release hydrogen peroxide in an aqueous solution, (c) Bleaching detergent composition containing one or more compounds selected from compounds represented by general formula (1) and general formula (2), and (d) one or more compounds selected from cyclodextrin and derivatives thereof Is to provide.

[Wherein, R ₁ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms, R ₂ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms, and M represents a hydrogen atom or a cation that forms a water-soluble salt. ]
Furthermore, the present invention provides a method for producing the above-mentioned bleaching detergent composition as a means for solving other problems, wherein (c) component and (d) component are mixed, and (d) component wraps (c) component. After obtaining the clathrate which contacted, the manufacturing method of the bleaching detergent composition which mixes with a clathrate, (a) component, and (b) component is provided.

Furthermore, the present invention provides a solution to other problems.
(A) component, (b) component, (c) In aqueous cleaning using a cleaning composition containing the component, (d) a cleaning method using the component as a bleaching power enhancer,
Alternatively, in the aqueous cleaning using the cleaning composition containing the component (a) and the component (b), a cleaning method using the inclusion body of the component (d) of the component (c) as a bleaching detergency enhancer is provided. To do.

  The composition of the present invention is excellent in bleaching detergency, and particularly when the inclusion body of the component (c) and the component (d) is contained, excellent bleaching detergency is exhibited.

<(A) component>
The composition of this invention contains 1 or more types of compounds chosen from surfactant as (a) component. Examples of the component (a) include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.

  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. In all the counter ions, the potassium ion is preferably 5% by mass or more, more preferably 20% by mass or more, and further preferably 40% by mass or more.

  Examples of the nonionic surfactant include ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl (poly) glycosides, and the like. . In particular, an EO average 1 to 10 mol adduct of an alcohol having 10 to 16 carbon atoms is preferable in terms of removal of sebum soil, hard water resistance, and biodegradability.

  Examples of the cationic surfactant include alkyltrimethylammonium salts, and examples of the amphoteric surfactant include carbobetaine-type and sulfobetaine-type amphoteric surfactants.

  The composition of the present invention preferably contains a nonionic surfactant as component (a) in terms of cleaning performance, and the nonionic surfactant in component (a) is preferably 10% by mass or more, and 30% by mass. % Or more is more preferable, and 50 mass% or more is still more preferable.

  In the composition of the present invention, an anionic surfactant is preferably used together with a 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 are preferable, 3/7 to 9/1 are more preferable, and 5/5 to 9/1 are still more preferable.

  The content of the component (a) in the composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 40% by mass in terms of cleaning performance and solubility. 20 to 35% by mass is particularly preferable.

<(B) component>
The composition of this invention contains 1 or more types of compounds chosen from the compound which discharge | releases hydrogen peroxide in aqueous solution as (b) component.

  As component (b), 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 (b) 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 the coating is preferably 5 to 20% by mass in the particles when used as the particles containing the component (b) in terms 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.

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

  The content of the component (b) 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.

<(C) component>
The composition of this invention contains 1 or more types of compounds chosen from the compound represented by above-described General formula (1) and General formula (2) as (c) component.

Among the compounds represented by the general formula (1) and the general formula (2), in terms of cleaning performance, the compound in which R ₁ in the general formula (1) is an alkyl group having 10 to 13 carbon atoms, and the general formula A compound in which R _{2 in} (2) is an alkyl group having 7 to 11 carbon atoms is preferred.

  Examples of the cation that forms a water-soluble salt include alkali metal ions, alkaline earth metal ions, ammonium salts, alkanolamine salts, and the like. Among them, sodium ions and potassium ions are preferable, and sodium ions are particularly preferable.

  In the composition of this invention, it is preferable to contain 1 or more types of compounds chosen from the compound represented by General formula (1) as a (c) component at the point of washing | cleaning performance.

  In the composition of the present invention, the component (c) is preferably in the form of particles containing the component (c) in order to enhance the stability. The amount of the component (c) in the particles containing the component (c) 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 (c) in the washing bath, the particles containing the component (c) 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.

  (C) The particle | grains containing a component may mix | blend the binder chosen from 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 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 in the particles containing the component (c).

  For the purpose of improving the stability of the particles containing the component (c), an acidic substance may be further added to 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 compounding amount of such an acidic substance is preferably 20% by mass or less, more preferably 1 to 15% by mass, and further preferably 1 to 10% by mass in the particles containing the component (c).

  The particles containing the component (c) can be obtained by mixing the above components by a desired method and then granulating with an ordinary granulator, and in particular, the surface activity for improving the solubility with the component (c). 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 (c) 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.

<(D) component>
The composition of the present invention contains one or more compounds selected from cyclodextrin and derivatives thereof. In the composition of the present invention, the component (d) may be used in such a form that when used in combination with the components (a), (b) and (c) described above, enhances the bleaching detergency. desirable.

  Examples of cyclodextrins include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, ε-cyclodextrin, ζ-cyclodextrin, η-cyclodextrin, θ-cyclodextrin, and the like. Derivatives include hydroxyalkylated cyclodextrins, alkylated cyclodextrins, glycosylated cyclodextrins, aminated cyclodextrins, carboxymethylated cyclodextrins, etc., wherein at least part of the glucose residue is hydroxyethyl, 2 -Chemically modified with hydrophilic functional groups such as hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxybutyl, 2-hydroxyisobutyl, diethylaminoethyl, trimethylammoniopropyl Mention may be made of cyclodextrin derivatives, cyclodextrin polymers polymerized with a crosslinking agent such as epichlorohydrin and polyvalent glycidyl ether, and branched cyclodextrins having branched side chains such as glucose and maltose.

  As the cyclodextrin and its derivatives, it is desirable that the component (c) can be included, and among them, α-cyclodextrin or β-cyclodextrin and its derivatives are preferable, and α-cyclodextrin and its derivatives are more preferable. preferable. Derivatives that have increased water solubility of cyclodextrins are preferred.

  The content of the component (d) in the composition of the present invention is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, and still more preferably 5 to 20% by mass in terms of cleaning performance.

  In the composition of the present invention, the components (c) and (d) are preferably in the form of particles composed of a mixture containing the components (c) and (d) in order to enhance the bleaching detergency. In this case, an inclusion body in which a part of the component (c) is included in the component (d) may be included. By adopting such a particle form, when the composition of the present invention is put into a washing bath, an inclusion body due to the component (d) of the component (c) is easily generated, which is preferable.

  In the composition of the present invention, in order to further enhance the bleaching detergency, the component (c) and the component (d) are encapsulated in which the component (d) includes part or all of the component (c), preferably all of them. It is preferable that it is a contact body. (C) A part of the component means a part of the used amount of the (c) component, and this includes only a part of the used amount of the (c) component mixed with the (d) component. In addition to the case where the inclusion body is generated, the case where the total inclusion amount of the component (c) and the component (d) are mixed and the case where the non-inclusion material remains is included.

  Thus, when the inclusion body by (d) component of (c) component was formed at the time of use, or when the said inclusion body was previously contained in the composition, it is nonionic as (a) component. In the case where a surfactant is included, bleach washing is performed in the washing bath because inhibition of peracid generation due to incorporation of the organic peracid precursor of component (c) into the micelle of the nonionic surfactant is suppressed. The power seems to be strengthened. Moreover, although the produced | generated organic peracid reacts with (c) component, it becomes impossible to use the produced | generated organic peracid effectively for the purpose of expressing bleaching performance, but (c) component and (d) component By forming the clathrate, the reaction between the generated organic peracid and the component (c) can be suppressed, so that it is considered that the bleaching performance is enhanced.

  In the composition of the present invention, in terms of cleaning performance, the mass ratio of the component (c) to the component (d) is preferably 1/1 to 1/20, more preferably 1/2 to 1/15, 4 to 1/10 is more preferable.

  In addition, as described above, when the inclusion body is formed from the component (d) of the component (c) during use, or when the inclusion body is previously contained in the composition, the bleaching detergency is enhanced. Therefore, the inclusion body by (d) component of (d) component or (c) component is applicable also to the following washing | cleaning method.

  As one cleaning method, in aqueous cleaning using a cleaning composition containing the components (a), (b), and (c), the cleaning method uses the component (d) as a bleaching detergency enhancer. Applicable.

  In this cleaning method, the component (a) is 0.003 to 0.03% by mass, preferably 0.006 to 0.03% by mass, and the component (b) is 0.0001 to 0.02% by mass, preferably 0.0005. To 0.01% by mass, (c) component 0.0003 to 0.03% by mass, preferably 0.0006 to 0.02% by mass with respect to the aqueous detergent system containing (c) component and (d ) Component (d) is added so that the ratio (mass ratio) of the component becomes the above-described ratio.

  As another cleaning method, in the aqueous cleaning using the cleaning composition containing the component (a) and the component (b), the inclusion body of the component (d) of the component (c) is used as a bleaching power enhancer. It can be applied to cleaning methods.

  In this cleaning method, the component (a) is 0.003 to 0.03% by mass, preferably 0.006 to 0.03% by mass, and the component (b) is 0.0001 to 0.02% by mass, preferably 0.0005. The concentration of the component (c) is 0.0003 to 0.03% by mass, preferably 0.0006 to 0.02% by mass, with respect to the aqueous detergent system containing ~ 0.01% by mass. The clathrate is added so that the ratio (mass ratio) of the component (d) to the component (d) is the ratio described above.

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

  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)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10) solution is prepared as a buffer solution. All sample solutions are prepared using this buffer. For measurement of 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.

  Other bleach activators include glucose pentaacetate, triacetin, N, N, N ′, N′-tetraacetylethylenediamine, tetraacetylglycolyluril, and compounds described in the following general formulas (3) and (4). Can be contained.

[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ are each independently an alkyl group or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ⁸ is a carbon number 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 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.

  The composition of the present invention is a mixture of the above-mentioned components (a) to (d) (can be granulated for each component as necessary) and other components, and granulated as necessary. In the above production process, after the (c) component and the (d) component are mixed, and the clathrate in which the (d) component includes part or all of the (c) component is obtained, Furthermore, it is preferable to comprise the process of mixing the said inclusion body with (a) component and (b) component.

(1) Production of powder bleach detergent composition A slurry having a solid content of 50% by mass was spray-dried at a hot air temperature of 250 ° C. to obtain the following base granules. Next, the surfactant mixture was supported on the base granules, and the surface was further modified to obtain the following detergent base.

  Next, a 0.1% (w / v) aqueous solution of (c) components I and II was prepared, and α-cyclodextrin as component (d) was dissolved therein to have a mass ratio shown in Table 1. . After dissolution, the aqueous solution was freeze-dried to prepare a powdery cyclodextrin mixture (mixture of components (c) and (d)).

  Next, according to the compounding quantity of Table 1, the detergent base containing (a) component, the mixture of (b) component, (c), and (d) component were mixed, and the powder bleach detergent composition was obtained.

<Base granule>
Composition: sodium polyacrylate (weight average molecular weight 10,000) 7 mass%, sodium carbonate 26 mass%, sodium sulfate 20 mass%, sodium chloride 6 mass%, fluorescent dye 0.5 mass%, zeolite 40 mass%, water 0 0.5% by mass. As the fluorescent dye, Chino Pearl CBS-X (manufactured by Ciba Geigy) was used. As zeolite, 4A type zeolite (manufactured by Tosoh Corporation) was used.

<Detergent base>
100 parts by mass of base granule I is put into a Redige mixer (Matsusaka Giken Co., Ltd., capacity 20 L, with jacket), and 20 parts by mass of nonionic surfactant (AE) is added under stirring of the main shaft (150 rpm). Chain alkyl (carbon number 10 to 13) sodium benzenesulfonate (LAS) 22 parts by mass, fatty acid (carbon number 14 to 18) sodium 4 parts by mass, polyethylene glycol (weight average molecular weight 8500) 2 parts by mass, water 4 parts by mass Was added in 3 minutes, followed by stirring for 5 minutes. Further, 20 parts by mass of crystalline sodium silicate and 10 parts by mass of zeolite were put into this mixer to perform surface coating. As the nonionic surfactant, polyoxyethylene alkyl ether having an alkyl group having 12 to 16 carbon atoms and EOp 6.0 was used. As the crystalline sodium silicate, powder SKS-6 (manufactured by Hoechst Tokuyama Corporation) was used.

  The obtained detergent base has a bulk density of 810 g / L, an average particle size of 270 μm, and a ratio of particles having a particle size of 177 to 350 μm of 55% by mass. Released from inside. The equilibrium relative humidity was 25% (40 ° C.).

<(B) Component-containing particles>
Sodium carbonate / hydrogen peroxide adduct (bleaching agent particles described in paragraph 0019 of JP-A No. 2000-256699)
<(C) Component I>
Sodium Lauroyloxybenzenesulfonate <(c) Component II>
Decanoyloxybenzoic acid (2) Bleaching detergency test 0.67 g of the composition prepared in (1) was dissolved in 1 liter of ion-exchanged water, and 5 pieces of 6 cm × 6 cm curry-stained cloth were placed in a targotometer. And washed at 100 rpm. The washing time was 10 minutes, the water temperature was 20 ° C., and rinsing was performed with tap water for 5 minutes.

  The curry-stained cloth was prepared by removing ingredients from 200 g of a commercially available curry with a retort pack using a coarse sieve, adding 100 g of ion-exchanged water, and stirring and mixing the mixture onto a cotton cloth. 0.4 g of curry was uniformly applied to each 6 cm × 6 cm cloth.

  The bleaching detergency was determined by measuring the reflectance at 460 nm of the untreated cloth and before and after washing with a self-recording colorimeter (manufactured by Shimadzu Corporation), and obtaining the bleaching washing rate (%) according to the following formula: The measured average value was shown as bleaching detergency. The results are shown in Table 1.

  Bleach washing rate (%) = [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)] × 100

The difference between the bleaching washing ratios of Examples 1 to 5 and Comparative Examples 2 and 3 is included in the detergent base because the component (c) and the component (d) form an inclusion body in the examples. In contrast, in Comparative Examples 2 and 3, the inclusion body was not formed, whereas the inhibition of organic peracid production by micelles of the nonionic surfactant as the component (a) was suppressed. .

Claims (5)

(A) a nonionic surfactant,
(B) one or more compounds selected from compounds that release hydrogen peroxide in an aqueous solution,
(C) 1 to 25 masses of one or more compounds selected from the compounds represented by general formula (1) and general formula (2), and (d) one or more compounds selected from cyclodextrin and derivatives thereof Containing,
The bleaching detergent composition whose mass ratio of (c) component and (d) component is 1/1 to 1/20.

[Wherein, R ₁ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms, R ₂ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms, and M represents a hydrogen atom or a cation forming a water-soluble salt. ]   The bleaching detergent composition according to claim 1, wherein the component (c) and the component (d) are in the form of particles comprising a mixture containing the component (c) and the component (d).   The bleaching detergent composition according to claim 1 or 2, wherein the component (c) and the component (d) are clathrate in which the component (d) includes part or all of the component (c).   It is a manufacturing method of the bleaching detergent composition of any one of Claims 1-3, (c) component and (d) component are mixed, (d) component is a part of (c) component, or A method for producing a bleaching detergent composition comprising obtaining a clathrate containing all of the clathrate and then mixing the clathrate with the component (a) and the component (b). (A) a nonionic surfactant, (b) one or more compounds selected from compounds that release hydrogen peroxide in an aqueous solution, (c) compounds represented by general formula (1) and general formula (2) In aqueous cleaning using a cleaning composition containing one or more compounds selected from:
(D) 1 to 25% by mass of one or more compounds selected from cyclodextrin and derivatives thereof, and a mass ratio of (c) component to (d) component is 1/1 to 1/20 as a bleaching detergency enhancer The cleaning method to use.

[Wherein, R ₁ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms , R ₂ represents an alkyl group or alkenyl group having 7 to 18 carbon atoms, and M represents a hydrogen atom or a cation forming a water-soluble salt. ]