JP2002294290A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching detergent composition which does not degrade clothes, exhibits high bleaching detergent effects, and is excellent in storage stability. SOLUTION: This bleaching detergent composition contains (a) a specific metal complex compound containing a macrocyclic tetraamide as a ligand and (b) a percarbonate. Compound (a) is compounded in the form of particles containing 0.1-95 mass% compound (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bleaching detergent composition.

[0002]

2. Description of the Related Art In recent years,
Oxygen bleaching agents such as hydrogen peroxide and inorganic peroxide have been used as cleaning agents for the purpose of removing stain stains and yellowing of underwear. Attempts have been made to use a bleaching catalyst to enhance the bleaching effect.

[0003] Bleaching catalysts have a very high bleaching effect, and a great deal of research has been conducted in recent years. JP-A-4-
Japanese Patent No. 216899 discloses that a manganese catalyst has an excellent bleaching effect. In addition, Tokio Table 10-51
No. 3215 discloses that a cobalt catalyst is useful as a hard surface bleach. However, bleaching catalysts often have an important problem of deteriorating clothing and the like during washing, and this improvement is strongly demanded.

For the purpose of improving the deterioration of clothing, Japanese Patent Laid-Open No. 9-2
Japanese Patent No. 5499 discloses a technique using a bleach catalyst and a clay mineral compound in combination. Japanese Patent Publication No. Hei 9-511774 discloses a technique in which a free radical-trapping antioxidant substance is used in combination. Japanese Unexamined Patent Publication (Kokai) No. 9-511775 discloses a laundry bleaching composition using a specific bleaching activator or the like and a metal complex in combination with less damage to a fabric. However, even these techniques cannot prevent the deterioration of clothing to a satisfactory level.

On the other hand, JP-T-2000-515194 discloses that a metal complex having a macrocyclic tetraamide as a ligand is useful as a bleaching catalyst. This catalyst is used for bleaching lignin in pulp,
It has been suggested that it can also be used as a household bleach. However, when this bleaching catalyst is applied to a domestic bleaching agent, there is a problem that not only a satisfactory bleaching washing effect cannot be obtained, but also a bleaching effect decreases during storage.

Accordingly, an object of the present invention is to provide a bleaching detergent composition which does not cause deterioration of clothing, has a high bleaching / cleaning effect, and is excellent in storage stability.

[0007]

According to the present invention, there are provided (a) a compound represented by the following general formula (1) (hereinafter, referred to as component (a)) and (b) a percarbonate (hereinafter, referred to as component (b)). A bleaching detergent composition containing (a) wherein (a) is 0.0%
The present invention relates to a bleaching detergent composition formulated as particles containing 1 to 95% by mass.

[0008]

Embedded image

[Where: R¹Is alkylene having 2 to 8 carbon atoms
Group, alkenylene group, phenylene group, cycloalkylene
Group, a cycloalkenylene group, preferably a phenylene group
Yes, R ^Two, R^Three, R^FourCan be the same or different
Each having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms.
Len or alkenylene or cycloalkyl
Group or cycloalkenylene group, or phenylene
Group, preferably an alkylene group having 1 to 3 carbon atoms. Ma
R¹, R^Two, R^Three, R^FourIs a hydroxy group,
Lucoxy group, halogen group, amino group, sulfate group, sulfone
Has substituents selected from acid groups, nitro groups and carboxylic acid groups
You may have. M is I, II, III, IV, V, VI, VII or
Is selected from transition metals having the oxidation state of VIII. X
Is any pair of ions that balances the charge of the compound on a stoichiometric basis.
Is on. ]

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION <(a) Component> The compound of the above general formula (1) used in the present invention is a compound represented by the general formula (1)
¹ is preferably an alkylene group or a phenylene group, more preferably a phenylene group, and particularly preferably an orthophenylene group. R ² and R ⁴ are preferably an alkylene group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. M is most preferably Fe, and X is an ammonium salt, particularly preferably a tetraalkylammonium salt having four alkyl groups having 2 to 10 carbon atoms bonded thereto. The compound of the general formula (1) is, for example,
The compound can be synthesized by the method described in JP-A-00-515152.

The component (a) of the present invention is blended with the compounds described below in the form of particles.
A granulated product obtained by granulating the compound of the general formula (1) with a binder material having tackiness or film forming property at a temperature of not lower than 30 ° C. and not melting at a temperature lower than 30 ° C. is preferable. The binder material has a melting point of 30 to 90 ° C, preferably 40 to 90 ° C.
A compound at a temperature of from 70 ° C. to 70 ° C. is preferred, and a compound selected from a polyalkylene glycol, a nonionic surfactant, a fatty acid and a polymer compound is particularly preferred.

The polyalkylene glycol is preferably polyethylene glycol, and has a weight average molecular weight of 200
0 to 20000, more preferably 4000 to 1000
A value of 0, particularly preferably 4000 to 8000, is good. Here, the weight average molecular weight is measured by gel permeation chromatography using polyethylene glycol as a standard substance.

As the nonionic surfactant, the average addition mole number of the alkylene oxide is 15 to 300, preferably 20 to 200, particularly preferably 20 to 150, and the alkyl group has 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms. Particularly preferred are 12 to 18 polyoxyalkylene (preferably polyoxyethylene) alkyl ethers.

As the fatty acid, a saturated fatty acid having 12 to 18, preferably 12 to 16 carbon atoms is preferred. These may be in the form of sodium or potassium soaps.

As the polymer substance, polyvinyl pyrrolidone, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, and polyhydroxyacrylic acid are preferable.

As the binder substance used in the particles containing the component (a) of the present invention, polyethylene glycol having a weight average molecular weight of 4,000 to 8,000 and polyethylene glycol having a carbon number of 12 to 16 are preferred in view of the solubility and storage stability of the component (a). One or more selected from saturated fatty acids are particularly preferred.

It is preferable to use 0.5 to 99.99% by mass, more preferably 1 to 99.99% by mass, particularly preferably 5 to 99.95% by mass of such a binder substance in the granulated product.

The particles containing the component (a) of the present invention preferably contain an anionic surfactant in order to improve the solubility of the compound of the formula (1) in a washing bath. Alkyl sulfates or polyoxyethylene alkyl ether sulfates or mixtures thereof are particularly preferred as anionic surfactants,
(A) In component, Preferably it is 0-50 mass%, More preferably, it is 5-45 mass%, Especially preferably, it is 10-40 mass%.
Mix. As the alkyl sulfate salt, an alkyl group having 10 to 18 carbon atoms, and an alkali metal salt such as a sodium salt is preferable, and sodium lauryl sulfate or sodium myristyl sulfate is particularly preferable. As the polyoxyethylene alkyl ether sulfate, a polyoxyethylene alkyl ether sulfate having an alkyl group having 10 to 18 carbon atoms is preferable, and a sodium salt is preferable. Here, the average degree of polymerization of the oxyethylene group (hereinafter the average degree of polymerization is indicated by POE) is 1 to 10, preferably 1 to 5.
And sodium polyoxyethylene lauryl ether sulfate (POE = 2 to 5) and sodium polyoxyethylene myristyl ether sulfate (POE = 2 to 5) are particularly good.

In the present invention, the above components can be mixed and granulated by any method. In addition, a preferable result can be obtained by melting and adding the binder substance in advance. The binder material is 40 to 100 ° C, preferably 50 to 100 ° C.
It is added by melting at 100 ° C., more preferably at 50-90 ° C. After stirring and mixing until they are uniform,
It is formulated by an ordinary granulator. Extrusion granulation can be mentioned as a preferable granulation method, and the average particle diameter is 500.
It is preferable to form granules having a size of from μm to 5000 μm, more preferably from 500 to 3000 μm. The component (a) of the present invention has an apparent specific gravity of 0.1 to 1.5 g / ml, preferably 0.1 to 1.5 g / ml.
4 to 1.0 g / ml, particularly preferably 0.4 to 0.9 g
/ Ml is good from the viewpoint of storage stability.

As another granulation method, tablet formation by a briquetting machine can be mentioned as a preferable granulation method. In addition, the granulation referred to in the present invention includes those in which the component (a) is coated and the surface is coated with other components.

The content of the compound of the general formula (1) as the component (a) in the particles is 0.01 to 99.5% by mass,
From the viewpoint of storage stability, the content is preferably 0.05 to 90% by mass, and more preferably 0.05 to 50% by mass.

The bleaching detergent composition of the present invention preferably contains 0.1 to 20% by mass, more preferably 0.1 to 10% by mass of the particles containing the component (a) in view of the storage stability and the bleaching effect. And the compound of the general formula (1) is contained in the composition in an amount of 0.0001 to 5% by mass, more preferably 0.0001 to 3% by mass.
It is preferable to mix them so that

<Component (b)> The component (b) is preferably sodium percarbonate (hereinafter abbreviated as PC), and more preferably is coated with a polymer, an inorganic salt or a solid inorganic acid. As a coated PC, for example,
No. 7-32200 (PC coated with paraffin), Japanese Patent Publication No. 53-15717 (PC coated with sodium perborate),
U.S. Pat. No. 4,131,562 [PC coated with sodium perborate and an ethylene oxide (hereinafter referred to as EO) adduct of alcohol], U.S. Pat.
C and sodium perborate coated with polyethylene glycol), German Patent 2712139 (PC coated with silicate), German Patent 2800916 (PC coated with boric acid), European Patent 30759 (PC coated with wax) JP-A-58-217599 (PC coated with borate), JP-A-59-196399 (PC coated with borate), JP-A-4-31498 (PC coated with boric acid and silica) And spraying with an acid salt separately) can be used.

In the present invention, in particular, (i) a percarbonate obtained by coating sodium borate, preferably sodium metaborate or sodium orthoborate at a ratio of 0.1 to 30% by mass based on the percarbonate; A) boric acid selected from orthoboric acid, metaboric acid and 4-boric acid in an amount of 0.3 to 20% by mass, preferably 0.5 to 10% by mass, based on percarbonate;
Particularly preferably, a percarbonate coated with 1 to 8% by mass, and (iii) sodium metasilicate, sodium orthosilicate,
Water glass No. 1, No. 2, No. 3, sodium salt, potassium metasilicate, potassium orthosilicate, preferably water glass
No. 2, No. 3 and No. 3 with S percarbonate
0.1 to 10% by mass, 0.2 to 7% by mass in terms of iO ₂ ,
Particularly preferred is a percarbonate coated with 0.3 to 5% by mass. Particularly, from the viewpoint of storage stability, percarbonate coated with both compounds (i) and (ii) is most preferable.

The percarbonate of the present invention can be produced by a usual method. As the coating method, a method in which a solution or powder containing the above-mentioned coating agent is mixed and adsorbed to the percarbonate in a wet state or a dry state and dried is used.

The component (b) of the present invention has an average particle diameter of 100 to 100.
It is preferably from 2000 μm, preferably from 250 to 1000 μm, from the viewpoint of the bleaching and washing effect.

Further, the bleaching detergent composition of the present invention comprises:
Component (b) is preferably 0.5 to 99% by mass, more preferably 1 to 95% by mass, and particularly preferably 1 to 90% by mass.
contains. The component (b) is preferably blended with particles different from the particles containing the component (a).

In the present invention, it is preferable to use a bleaching activator (hereinafter, referred to as a component (c)) in combination for the purpose of further improving the bleaching and washing effect. Specific preferred compounds include tetraacetylethylenediamine, having 5 to 15 carbon atoms.
Alkanoyloxybenzene sulfonic acid and carbon number 5
A bleaching activator selected from alkanoyloxybenzenecarboxylic acids or salts thereof. Specific preferred compounds include octanoyloxy-p-benzenesulfonate, nonanoyloxy-p-benzenesulfonate, decanoyloxy-p-benzenesulfonate, dodecanoyloxy-p-benzenesulfonate, and octanoyloxy-p-benzenesulfonate. Noyloxy-p- (or-o-) benzenecarboxylic acid or a salt thereof, nonanoyloxy-p- (or-o-) benzenecarboxylic acid or a salt thereof, decanoyloxy-p- (or-o-) benzenecarboxylic acid Or a salt thereof, dodecanoyloxy-p- (or -o-) benzenecarboxylic acid or a salt thereof, particularly nonanoyloxy-
P-benzenesulfonate, decanoyloxy-p-benzenesulfonate, dodecanoyloxy-p-benzenesulfonate, decanoyloxy-p-benzenecarboxylic acid or a salt thereof is preferred. Noyloxy-p-benzenesulfonate is most preferred.

Examples of the salt include a sodium salt, a potassium salt, a magnesium salt, an alkanolamine salt and an ammonium salt, and a sodium salt, a potassium salt and a magnesium salt are preferable from the viewpoint of solubility.

The bleach activator may be blended with the same particles as the component (a), or may be separately granulated and granulated to dry blend with other particles. When granulating, for example, the method described in JP-A-8-3593 can be used.

The bleaching detergent composition of the present invention contains component (c) in an amount of preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 5% by mass.
contains.

[0032] The bleaching detergent composition of the present invention preferably contains a surfactant for the purpose of improving the bleaching washing effect. As a specific example, the carbon number of the alkyl group is 10 to 2
0, preferably 10 to 15 alkyl benzene sulfonates, wherein the alkyl group has 8 to 18 carbon atoms, preferably 10 to 10 carbon atoms.
And at least one anionic surfactant selected from polyoxyethylene alkyl ether sulfates having 8 to 18, preferably 10 to 14 carbon atoms in the alkyl group. The average number of moles of EO added to the polyoxyethylene alkyl ether sulfate is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. As a counter ion of these anionic surfactants, alkali metals such as sodium and potassium are preferable. Further, an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant other than the above may be blended. Specific examples include olefin sulfonates, alkane sulfonates, fatty acid salts, alkyl or alkenyl ether carboxylates, α
Anionic surfactants such as sulfo fatty acid salts, α-sulfo fatty acid esters, polyoxyethylene or polyoxypropylene or copolymers thereof, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or Non-ionic surfactants such as alkylene oxide adducts, sucrose fatty acid esters and alkyl glycosides; amphoteric surfactants such as amine oxides, sulfobetaines and carbobetaines; and cationic surfactants such as quaternary ammonium salts. Can be Especially 10 to 2 carbon atoms
A polyoxyethylene alkyl or alkenyl ether having 0, preferably 10 to 18 alkyl or alkenyl groups and an average degree of condensation of 4 to 20, preferably 4 to 15 polyoxyethylene chains in the molecule;
It is preferable to blend a fatty acid having an alkyl group composition of 18, preferably 10 to 18 or an alkyl group derived from coconut oil or tallow, or a sodium or potassium salt thereof. In the present invention, the amount of the surfactant is preferably 0.1 to 60% by mass, more preferably 0.1 to 5% by mass in the composition in terms of bleaching detergency and foamability.
0 mass%, particularly preferably 0.5 to 40 mass%.

The bleaching detergent composition of the present invention preferably contains an alkali metal carbonate in order to enhance the bleaching washing effect. As the alkali metal carbonate, a sodium salt is preferable in terms of stability, and examples thereof include sodium carbonate, sodium bicarbonate, and sodium sesquicarbonate. Most preferred is sodium carbonate, which may be separately dry-blended with bleach activator particles or inorganic peroxide, in which case the average particle size is 100-500 μm.
m are preferably used. Further, a slurry or a kneaded intimate mixture may be formed together with a surfactant, zeolite and other cleaning aids, and the mixture may be blended as particles of a detergent cloth obtained by drying the mixture.
The alkali metal carbonate is preferably contained in the bleaching detergent composition in an amount of 0.5 to 60% by mass, more preferably 1 to 50% by mass.

The bleaching detergent composition of the present invention preferably contains a silicate. Silicates include amorphous sodium silicates such as Nos. 1 to 3 sodium silicate, and JP-A-7-89712.
No. JP-A-60-227895 and Phys. C
hem. Glasses. 7, p127-p138 (1966), Z. Kristallogr.,
129, p396-p404 (1969)
And product name "Na-SKS-6" from Clariant
Crystalline sodium silicate commercially available as (δ-Na ₂ Si ₂ O ₅ ) is preferred.

The silicate referred to in the present invention has a maximum pH of 11 when dispersed by 0.1% by mass in ion-exchanged water at 20 ° C.
This is excellent in alkali ability that requires 5 ml or more of 0.1N HCl aqueous solution to bring the pH to 10 with respect to 1 L of the dispersion, and is distinguished from crystalline aluminosilicate which is a zeolite. You.

The amorphous silicate is blended with the above-mentioned surfactant, alkali metal carbonate, and other cleaning aids in a detergent cloth, or is separately granulated and dry-blended to prepare a bleaching detergent composition. When incorporated as a detergent fabric, amorphous silicate is preferred because it acts as a skeletal forming agent that strengthens the particles. In addition, the crystalline silicate is preferably dry-blended with the bleaching detergent composition so as not to impair the ion exchange ability. The silicate is preferably present in the bleaching detergent composition in an amount of 0.1 to 20.
%, More preferably 0.5 to 10% by mass.

In the present invention, a polymer component is preferably blended in order to improve the bleaching / cleaning performance. Examples of the polymer component include homopolymers such as polyacrylic acid, polymethacrylic acid and polyhydroxyacrylic acid, and acrylic acid and maleic acid. In addition to carboxylic acid-based polymers such as copolymers of the above, non-ionic polymers such as polyethylene glycol can be exemplified. Among them, polyacrylic acid or polyhydroxyacrylic acid having a weight average molecular weight of 5,000 to 20,000 or a salt thereof, acrylic acid / maleic acid having a weight average molecular weight of 30,000 to 80,000 (molar ratio 2/8 to 8/2), and And polyethylene glycol having a weight average molecular weight of 4,000 to 10,000. The compounding amount of these polymers is preferably 0.05 to 20% by mass in the composition, more preferably 0.1 to 20% by mass.
10% by mass.

In the present invention, it is preferable to mix enzymes such as cellulase, protease, and lipase. Particularly, the alkalophilic microorganism Bacillus sp. KSM-635 (F
The use of alkaline cellulase produced from ERM BP-1485) or a mutant thereof is preferred for the purpose of further improving the bleaching and washing effect. This alkaline cellulase has an optimum pH of 7 or more when carboxymethylcellulose is used as a substrate, or a relative activity at a pH of 8 or more is 50% or more of the optimum condition. As a commercially available enzyme granulated product, specifically, KAC500 (Kao Corporation)
Manufactured).

In the present invention, it is preferable to add an alkaline protease. Examples of such proteases include Bacillus sp. KSM-K16 (No. 11418, Bacillus sp.) And Bacillus sp. KSM-K.
Alkaline protease produced from No. 14 (Microtechnical Laboratories No. 12587) is good. Commercially available proteases include Alcalase, Savinase (Novo Nordic), Maxapem (Genencor),
KAP4.3G (manufactured by Kao Corporation) and the like.

The enzyme used in the present invention is preferably blended in the form of granulated enzyme powder obtained by drying a concentrated solution obtained by filtering and concentrating a culture solution. The content of the enzyme powder in the granulated product is preferably as follows. 0.5 to 30% by mass, more preferably 0.8 to 25% by mass is preferable from the viewpoint of stability. Further, such an enzyme granule is preferably contained in the bleaching detergent composition in an amount of 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, particularly preferably 0.3 to 5% by mass.

The bleaching detergent composition of the present invention can reduce the concentration of calcium, magnesium and the like in tap water,
The average particle size for improving the powder physical properties of the particles is 0.1 to
Metal ion exchangers such as 10 μm A-type or P-type zeolite, ethylenediaminetetraacetate, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonate which suppresses the decomposition of bleaching species by heavy metals, etc. Metal ion supplements, antifoaming agents in which silicone oil and silica are carried on polyethylene glycol or cellulose compound, sodium sulfate (sodium sulfate) as an extender for detergent fabrics, other fluorescent dyes, fragrances, etc. .

In the present invention, the above-mentioned detergent component can be used in the form of a powder or a lump, and the method for producing the composition is not particularly limited, and a conventionally known method can be used. Preferably, it is a granular composition having a high bulk density. The high bulk density is, for example, a method of spraying a nonionic surfactant onto spray-dried particles of a detergent to increase the density, or while directly storing the nonionic surfactant in a powder component containing an oil absorbing carrier. A method of increasing the density can be used. Specifically, JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, and JP-A-2-22
2498, JP-A-2-222499, JP-A-3-33199, JP-A-5-86400, JP-A-5-209200, JP-A-9-876
No. 90 and WO 99/29830. In addition, zeolite is (a)
A small amount may be added during granulation or shortly before the end of granulation for use as a surface modifier of the component particles, preferably the granulated product. When a crystalline silicate is blended, it is preferable to add the crystalline silicate at the time of increasing the bulk density or to add the crystalline silicate by dry blending. When the alkali metal carbonate is blended, it may be added to the slurry, during granulation or in the dry blend.

The average particle size of the bleaching detergent composition of the present invention is as follows:
200 to 1000 μm to obtain preferable powder properties,
In particular, the thickness is desirably 200 to 600 μm. Also,
The bulk density of the bleaching detergent composition of the present invention is 0.5 to 1.2 g.
/ Cm ³ , preferably 0.6 to 1.0 g / cm ³ .

The bleaching detergent composition of the present invention is adjusted to a concentration suitable for each washing depending on washing methods such as washing machine washing and pickling washing, as well as the amount of clothes and water, the degree of dirt, and the use of machines. Can be used. For example, it is preferable to use a concentration of 0.03 to 0.3% by mass in the case of washing with a washing machine, and a concentration of 0.1 to 2% by mass in the case of immersion washing.

[0045]

EXAMPLES Granules were prepared from the following compounds according to the following production examples.

[0046]

Embedded image

AS: sodium lauryl sulfate ester ES: sodium polyoxyethylene lauryl ether sulfate (average number of moles of added EO: 3) POEO: lauryl alcohol containing EO in an average of 2 mol;
PO added on average at 3 mol, EO added on average at 3 mol, and added in block order in this order. PEG: polyethylene glycol (weight average molecular weight 8
・ FA; myristic acid ・ succinic acid.

Production Example 1-1 (Production of granulated product a-1) A high-speed mixer (FS) manufactured by Fukae Kogyo Co., Ltd. was prepared so that the total amount of the bleaching catalyst (A) 5 parts by mass and PEG 95 parts by mass was 5000 g in total. -GC-10 type)
And FA used were previously melted at 80 ° C.). The powder was mixed and heated at a jacket temperature of 80 ° C., a main shaft rotation speed of 200 rotations / minute, and a crushing blade rotation speed of 1500 rotations / minute, and was withdrawn when the powder temperature reached 70 ° C. Next, the obtained mixture was extruded with a granulator (Fuji Paudal Co., Ltd.)
Pelleter double EXD-100 type) with hole diameter 800
Extruded through a μm screen. After cooling the obtained extrudate with a vibrating cooler (Vibro / Flow Dryer VDF / 6000 type, manufactured by Fuji Paudal Co., Ltd.), a knife cutter F manufactured by Fuji Paudal Co., Ltd.
(L-200 type). The obtained pulverized product was classified to obtain a granulated product a-1 having an average particle size of 900 μm.

Production Example 1-2 (Production of granulated product a-2) Granulated product a-2 was produced in the same manner as in Production Example 1-1 except that the bleaching catalyst (A) was changed to the bleaching catalyst (B). Was manufactured.

Production Example 1-3 (Production of granulated product a′-1) Granulated product a ′ was produced in the same manner as in Production Example 1-1 except that the bleaching catalyst (A) was changed to the bleaching catalyst (C). -1 was prepared.

Production Example 2-1 (Preparation Method of Coated Sodium Percarbonate PC-1) 1,000 g of PC having an average particle diameter of 500 μm was put into a stirring mixer and stirred at 250 rpm, and 25% of sodium metaborate tetrahydrate was added. No.-1 water glass sodium salt 10
% Aqueous solution was sprayed, stirred for 10 minutes, and dried with hot air to produce coated sodium percarbonate PC-1 (P
0.4 mass% of sodium metaborate with respect to C, 0.16 mass% of sodium salt of No. 1 water glass). Average particle size is 4
It was 50 μm.

Production Example 2-2 (Preparation method of coated sodium percarbonate PC-2) 10 kg of PC having an average particle diameter of 500 μm was sprayed through a spray nozzle 2
The PC was placed on a perforated plate of a fluidized-bed dryer equipped with the apparatus, and hot air at 105 ° C. was sent from below to bring the PC into a fluidized state. A 15% aqueous solution of boric acid was sprayed at a flow rate of 80 g / min from the spray nozzle, and a water glass No. 1 aqueous solution having a concentration of 15% by mass in terms of SiO ₂ was simultaneously sprayed from another spray nozzle at a flow rate of 20 g / min. Spraying was continued while flowing and drying for 33 minutes to obtain coated sodium percarbonate PC-2 having an average particle size of 460 μm (4% by mass of boric acid based on PC, 1% by mass as SiO ₂ ). Production of granules c-1) The raw materials charged into the high-speed mixer were 70 parts by mass of sodium dodecanoyloxybenzenesulfonate, POE
O5 parts by mass, ES5 parts by mass, succinic acid 5 parts by mass, PEG
Granulated product c-1 was produced in the same manner as in Production Example 1-1 except that the amount was 15 parts by mass.

Production Example 4 (Production of detergent cloth) 2 kg of sodium straight-chain alkylbenzene sulfonate (alkyl group having 12 carbon atoms), 0.5 kg of sodium lauryl sulfate, polyoxyethylene alkyl ether (12,13 carbon atoms) 0.3 kg of EO added to a primary branched alcohol of an average of 10 mol), 0.3 kg of an acrylic acid-maleic acid copolymer (of a molar ratio of 80:20, weight average molecular weight of 40,000), a fatty acid salt (tallow, Na salt) 0.3 kg, sodium carbonate 0.6 kg,
No. 1 sodium silicate 1.5kg, 4A type zeolite (average particle size 0.3μm) 1.5kg, sodium sulfate 0.4kg, P
A water slurry having a solid content of 60% was prepared from 0.1 kg of EG, and spray-dried the obtained slurry to obtain particles obtained by Fukae Industry Co., Ltd.
Granulation in a high-speed mixer (model FS-GC-10) made of Detergent (with an average particle size of 400 μm and a bulk density of 75)
0 g / L).

EXAMPLES Granules prepared by the above method, coated sodium percarbonate,
Using the detergent fabric, the bleaching detergent compositions shown in Table 1 of Table 1 were prepared. 50 g of these compositions were placed in a wide-mouthed standard bottle PS-No13K and stored in a constant temperature room at 40 ° C. for 30 days. The bleaching and cleaning effect of the composition before and after storage was measured by the following method.
The effect of the composition before storage on deterioration of clothing was evaluated by the following method. Table 1 shows the results.

<Bleaching effect> 10 g of the composition shown in Table 1
Was dissolved in 2 L of tap water, and five pieces of curry-stained cloth prepared as described below were immersed in the solution for 60 minutes. Thereafter, it was rinsed with tap water, dried and the bleaching ratio was calculated by the following formula.

[0056]

(Equation 1)

The reflectance was NDR-1 manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured using a 460 nm filter at 01DP.

* Preparation of Curry-Contaminated Cloth After the solid content of retort curry (curry Marche) made of house food was removed with a mesh, the obtained liquid was heated to boiling. Soak a cotton cloth # 2003 in this solution,
Boil for a minute. The mixture was taken down from the fire 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. After pressing, 10cm × 10
The test piece was used as a test piece of cm.

<Effect of Preventing Clothing Deterioration> Five red polo shirts (Polo shirt S-701 red, manufactured by Shinmen Co., Ltd.) are shown in Table 1.
(Toshiba 2-tub washing machine VH-
360S1, the composition concentration in Table 1 was 0.0667% by mass, 30 L of tap water was used, the water temperature was 20 ° C., the washing was performed for 10 minutes, and after dehydration for 1 minute, 30 L of tap water was injected and rinsed for 5 minutes. After dehydration, it was naturally dried indoors). The condition of the clothing after repeating the washing 30 times was determined according to the following criteria. The average score of 5 sheets was obtained, and the average score of 1 or more and less than 2 was evaluated as ○, 2 or more
The results are shown in Table 2 as □ when less than 5 and Δ when 2.5 or more and less than 3.5.

Judgment Criteria 1: Almost no difference from new clothing 2: Slightly faded but not so noticeable

3: Fading, fiber damage such as fraying of cuffs is observed. 4: Remarkable fading and fiber damage is observed. 5: Remarkable damage such as tearing of clothing is observed.

[0062]

[Table 1]

KAP4.3G: Protease (manufactured by Kao Corporation) KAC500: Cellulase (manufactured by Kao Corporation) Sodium carbonate: dense ash PC: Uncoated sodium percarbonate manufactured by Nippon Peroxide Co., Ltd. Bleaching Catalyst (A): The bleaching catalyst (A) powder itself (non-particulate) was added to the composition.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masakazu Furukawa 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4H003 AB03 AB19 AB27 AB31 AC08 AC23 BA10 DA01 EA12 EA15 EA16 EA28 EB26 EB32 EB36 EC02 EC03 EE05 FA15 FA16 FA43

Claims (1)

[Claims] 1. A bleaching detergent composition comprising (a) a compound of the following general formula (1) and (b) a percarbonate,
A bleaching detergent composition wherein (a) is blended as particles containing 0.01 to 95% by mass of (a). Embedded image [Wherein R ¹ is an alkylene group having 2 to 8 carbon atoms, alkenylene group, phenylene group, cycloalkylene group, cycloalkenylene group, and R ² , R ³ and R ⁴ may be the same or different, It is a C1-C8 alkylene group, alkenylene group, cycloalkylene group, cycloalkenylene group, or phenylene group, respectively.
R ¹ , R ² , R ³ and R ⁴ each represent a hydroxy group,
It may have a substituent selected from an alkoxy group, a halogen group, an amino group, a sulfate group, a sulfonic group, a nitro group and a carboxylic group. M is I, II, III, IV, V, VI, VII
Or a transition metal having an oxidation state of VIII.
X is any counter ion that balances the charge of the compound on a stoichiometric basis. ]