JP2002020793A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition having high bleaching power and detergency excellent in preservation stability (caking resistance). SOLUTION: This detergent composition includes (a) 5-50 wt.% of a surfactant, (b) 0.1-10 wt.% of particles producing hydrogen peroxide in aqueous solution, (c) 0.05-5 wt.% of an activator for bleaching and (d) 0.5-30 wt.% of a chelating agent having 3-5 carboxyl groups in the molecule, 600 or less of molecular weight and 6-13 of chelate stability constant with Ca2+. N,N-bis(carboxymethyl)-2-aminopentane diacid or the like are enumerated as the chelating agent (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to detergent compositions.

[0002]

2. Description of the Related Art Detergent compositions are strongly directed to higher bulk densities and lower usage in consideration of consumer convenience and environmental considerations. In addition, there is a trend toward water saving, low-temperature washing, and shortening of washing time from the consumer needs of "I want to finish the laundry easily" and "I want to wash my clothes carefully" and responding to the environment, energy and economy. .

[0003] Various stains adhere to clothes and the like in daily life. Under such a change in the washing environment, washing with a normal detergent alone removes so-called stains such as blood stains, food stains, and plant stains. The power is not enough. In addition, residual sebum that cannot be completely removed by ordinary washing causes yellowing of clothing during storage.

[0004] Since bleaching agents are very effective against such stains, it has been attempted to add bleaching components to detergents. Bleaching components are roughly classified into oxygen-based and chlorine-based. Examples of the chlorine type include hypochlorous acid and dichlorocyanuric acid. These have problems with stability, smell, etc.
In addition, it is not suitable for detergent formulation, and because of its strong bleaching power, it has to be nervous for colored or patterned clothing.

[0005] Oxygen-based bleaching agents have a slight decrease in bleaching power at room temperature as compared with chlorine-based bleaching agents, but do not lose color when applied to colored or patterned clothing, do not impair the fabric, and yellow. It is widely used in powder detergents because it does not.

[0006] However, oxygen-based bleaching is unstable and has problems such as a decrease in activity during storage. In addition, when trace metals such as iron and copper are present as impurities, the decrease in the activity of the oxygen bleach is further accelerated because these act as catalysts. Also, as a detergent builder (sequestering agent), a phosphorus compound such as sodium tripolyphosphate was once compounded. At present, zeolite which is crystalline sodium aluminosilicate having a specific structure is a main component of the sequestering agent. However, since zeolite also acts as a catalyst,
In a detergent containing zeolite, the oxygen bleaching agent becomes very unstable and rapidly loses available oxygen due to the catalytic decomposition action of the zeolite. Also, this zeolite may not be able to exhibit sufficient performance with low-temperature, short-time washing. In order to compensate for such a lack of detergency of the zeolite, a polymer dispersant such as a polycarboxylic acid-based polymer is generally blended in the detergent. This polycarboxylic acid-based polymer is a kind of ion exchanger like zeolite, and has a function of blocking polyvalent cations. Since this builder is water-soluble, it is effective in sequestering polyvalent cations at low water temperature, but has a problem of insufficient biodegradability.

[0007] In recent years, build-ups with good biodegradability and excellent sequestering performance have been studied due to increasing interest in environmental influences. Against this background,
Some specific organic builders and cleaning compositions containing these are disclosed in JP-A-50-3979 and JP-A-55-157.
No. 695, JP-A-55-160099, JP-A-56-16099.
No. 81399, WO9612784, WO96304
No. 79 and US Pat. No. 3,675,511, and describe that these builders are excellent in biodegradability and detergency. However, when these specific organic builders are incorporated into a detergent in the form of a high-performance metal salt, the resulting detergent has high hygroscopicity and has a problem in the storage stability (caking resistance) of the resulting detergent. In particular, a powder detergent containing an oxygen-based bleaching agent has a problem that the activity of the oxygen-based bleaching agent is reduced by moisture absorption.

[0008] If the oxygen-based bleaching agent can be stably incorporated into the detergent, bleaching can be performed at the same time as washing, which is convenient. Therefore, there is a strong demand for the development of a technology for improving the storage stability of the oxygen-based bleaching agent. It is rare.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition having high bleaching detergency and excellent storage stability (caking resistance).

[0010]

The present invention relates to (a) a surfactant (hereinafter referred to as a component (a)) of 5 to 50% by weight;
Particles releasing hydrogen peroxide in an aqueous solution [hereinafter referred to as component (b)] 0.1 to 10% by weight, (c) bleach activator [hereinafter referred to as component (c)] 0.05 to 5% by weight and ( d) 1
It has 3 to 5 carboxyl groups in the molecule and has a molecular weight of 60
0 or less, a chelating agent comprising a compound having an average degree of neutralization of 20 to 70% and a chelate stability constant with Ca ^{2+ of 6} to 13 [hereinafter referred to as component (d)] containing 0.5 to 30% by weight. Detergent composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [(a) Component] The (a) component is 5 to 50% by weight, preferably 15 to 50% by weight, more preferably 20 to 48% by weight, and 25% by weight.
It is more preferably from 45 to 45% by weight, particularly preferably from 35 to 40% by weight. It is not less than 5% by weight in terms of cleaning performance and not more than 50% by weight in terms of dissolution rate.

The component (a) includes an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a cationic surfactant and the like.

Examples of the anionic surfactant include a sulfate of a higher alcohol, a sulfate of an ethoxylated higher alcohol, an alkylbenzene sulfonate,
Examples thereof include a paraffin sulfonate, an α-olefin sulfonate, an α-sulfofatty acid salt or an ester salt thereof, and a fatty acid salt. In particular, when the carbon number of the alkyl chain is 1
A linear alkylbenzene sulfonate having 0 to 18 (preferably 12 to 14) and an alkyl ester salt of α-sulfofatty acid having 10 to 20 carbon atoms are preferable. Examples of the counter ion include an alkali metal, an alkaline earth metal, ammonium, and an alkanolamine. From the viewpoint of adjusting the dissolution rate, it is also preferable to use potassium ions in combination. The potassium ion in all the counter ions is preferably 5% by weight or more, more preferably 20% by weight or more, and particularly preferably 40% by weight or more.

Examples of the nonionic surfactant include an ethylene oxide (hereinafter referred to as “EO”) adduct of a higher alcohol or EO / propylene oxide (hereinafter referred to as “PO”).
Adducts), fatty acid alkanolamides, alkyl (poly) glycosides and the like. Especially when the carbon number is 10
An adduct of an average of 1 to 10 moles of an EO with an alcohol of from 16 to 16 is preferred in terms of removing sebum stains, hard water resistance, biodegradability, and compatibility with a linear alkylbenzene sulfonate.

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

[Component (b)] As the component (b), carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct, tripolyphosphate / hydrogen peroxide adduct, pyrophosphate / peroxide Hydrogen adducts, urea / hydrogen peroxide adducts and the like can be mentioned. Among these, carbonate / hydrogen peroxide adduct, borate / hydrogen peroxide adduct are preferable, and sodium carbonate / hydrogen peroxide adduct and sodium borate / hydrogen peroxide adduct are more preferable.

The component (b) is preferably coated with an inorganic or organic compound from the viewpoint of storage stability. As inorganic compounds, sodium carbonate, sodium sulfate, magnesium sulfate, magnesium silicate, magnesium chloride,
Examples include magnesium oxide and sodium silicate, and examples of the organic compound include polyethylene glycol, polyvinylpyrrolidone, and hydroxypropylcellulose. For example, it can be produced by the method described in JP-A-59-196399.

The content of the component (b) is from 0.1 to 0.1% in the composition.
10% by weight, preferably 0.5 to 8% by weight,
5% by weight is more preferred. 0.1% by weight in terms of bleaching effect
This is not more than 10% by weight in terms of detergency.

[Component (c)] The content of the component (c) is 0.05 to 5% by weight in the composition.
0.1 to 2% by weight is preferred, and 0.5 to 1.5% by weight.
% Is more preferred. 0.05% by weight in terms of bleaching effect
This is not more than 5% by weight in terms of efficiency.

The component (c) is a bleaching agent such as glucose pentaacetate, triacetin, N, N, N ', N'-tetraacetylethylenediamine, tetraacetylglycoluril, etc., which is generally used in an oxygen-containing bleach-containing detergent. Although an activator can be used, compounds represented by the general formulas (1) to (4) are particularly preferable from the viewpoint of effects.

[0021]

Embedded image

Wherein R ₁ is an alkyl group having 4 to 13 carbon atoms, preferably 10 to 13 carbon atoms, R ₂ is an alkyl group having 5 to 13 carbon atoms, preferably 7 to 11 carbon atoms, and M is a hydrogen atom or an alkali metal. , Alkaline earth metal, ammonium or alkanolamine. ]

[0023]

Embedded image

[Wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ ,
R ₁₀ is independently an alkyl group (preferably methyl group, ethyl group) of 1 to 5 carbon atoms or a hydroxyalkyl group (preferably a hydroxyethyl group), R ₈
Is an alkylene group having 2 to 10 carbon atoms, and X ^- is an anion (preferably a halogen ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion, a phosphate ion or a sulfate ion having 1 to 12 carbon atoms). Show. ].

The component (c) is preferably blended as a granulated product. In order to improve the solubility, the composition preferably contains, for example, an anionic surfactant or a nonionic surfactant used as the component (a). Particularly, a sulfate of a higher alcohol, a sulfate of an ethoxylated higher alcohol, or an E of a higher alcohol
O adducts or mixtures thereof are preferred. The content of the anionic surfactant or the nonionic surfactant is preferably 5 to 45% by weight, more preferably 10 to 40% by weight in the granulated product. The granules can be formulated using one or more binder substances selected from polyethylene glycol, fatty acids and salts thereof. The content of the binder substance is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight in the granulated product.

[Component (d)] The content of the component (d) is 0.5 to 30% by weight in the composition.
And preferably 1 to 25% by weight, more preferably 1.5 to 20% by weight, and still more preferably 2 to 15% by weight. It is 0.5% by weight or more in terms of the chelating effect, and 30% by weight or less in terms of detergency.

The average degree of neutralization of the component (d) is 20 to 70%,
Preferably it is 30 to 60%. If the average degree of neutralization of the chelating agent is less than 20%, the solubility of the powder decreases, and as a result, sufficient cleaning performance cannot be obtained. On the other hand, if it is larger than 70%, the hygroscopicity is increased, and the powder properties such as the caking resistance are deteriorated, which makes the handling difficult. Here, the “average degree of neutralization” is an average of the degree of neutralization of an acid-type chelating agent with an alkali, and is represented by the following equation.

[0028]

(Equation 1)

The molecular weight of the component (d) is 600 or less, and the number of carboxyl groups contained in one molecule is 3
~ 5. (D) the molecular weight of the component is greater than 600,
If the number of carboxyl groups contained in one molecule is 6 or more, the amount of metal captured per gram of the chelating agent will decrease. On the other hand, if the number of carboxyl groups contained in one molecule is 2 or less, sufficient chelating power cannot be obtained.

Further, the component (d) is a chelate stability constant with Ca ²⁺ (hereinafter referred to as a Ca chelate stability constant).
Is 6 to 13. Here, the “chelate stability constant” is an index of the chelating power, and a detergent composition satisfying both the detergency and the hygroscopicity can be obtained by using the above range. In the present invention, the Ca chelate stability constant is determined by the following method.

<Method of Measuring Ca Chelate Stability Constant> 0.1 mol / L of NH ₄ Cl—NH ₄ OH was used as a buffer.
Prepare a solution (pH 10.0). All sample solutions were prepared using this buffer. For measurement of Ca ²⁺ concentration,
An ion meter 920A manufactured by Orion and a Ca ²⁺ ion electrode were used. First, the relationship between the calcium chloride concentration and the potential of the electrode is determined, and a calibration curve is created. 5.36 × 10 ⁻² mol / L solution of calcium chloride, chelating agent sample
A 36 × 10 ⁻⁴ mol / L solution is prepared. 1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution,
Stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The chelating agent is 1: 1 with Ca ²⁺
Assuming that a chelate complex is formed with
Find the chelate stability constant.

[0032]

(Equation 2)

As a chelating agent that satisfies all the above conditions, an aminopolycarboxylic acid represented by the following structure is preferable.

[0034]

Embedded image

[Wherein R ₁₁ is — (CH ₂ ) _n -A;
A is a hydrogen atom, a hydroxyl group or COOM ₁ , M ₁ is a hydrogen atom, an alkali metal (preferably Na, K) or ammonium, and n represents 0 to 3. ].

As the chelating agent to be blended in the present invention, N, N-bis (carboxymethyl) -2-aminopentanedioic acid, N, N
N-bis (carboxymethyl) -2-aminobutanedioic acid, N, N-bis (carboxymethyl) -2-aminopropanoic acid, N, N-bis (carboxymethyl) -2-amino-3-hydroxypropanoic acid and the like The partially neutralized alkali salt of bis (carboxymethyl) amino acid is preferred. Since these are all excellent in biodegradability, they are also preferable for the environment.

[Others] The detergent composition of the present invention comprises, as other components, inorganic builder, alkali agent, water-soluble polymer, anti-redeposition agent, softening agent, fluorescent brightener, and foam known in the field of detergents. Control agents, enzymes, perfumes and the like can be included.

As the inorganic builder, crystalline aluminosilicate, amorphous aluminosilicate, crystalline sodium silicate,
Examples thereof include sodium tripolyphosphate and sodium pyrophosphate, and a crystalline aluminosilicate is more preferable from the viewpoint of environmental impact and cleaning performance. From the viewpoint of cleaning performance, 10 to 50% by weight is preferable, and 15 to 40% by weight is more preferable.

Examples of the alkaline agent include carbonates, silicates, amines (such as alkylamines and alkanolamines), and more preferably carbonates and silicates. From the viewpoint of cleaning performance, 5 to 50% by weight is preferable, and 10 to 40% by weight is more preferable.

Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, and saccharides. Among them, a carboxylic acid-based polymer having a molecular weight of 1,000 to 100,000 is preferable in terms of sequestering ability of metal ions, dispersing ability of solid dirt / particle dirt, and ability of preventing re-contamination. Particularly, a salt of an acrylic acid-maleic acid copolymer and a polyacrylate are preferred. Here, examples of the salt include an alkali metal salt such as a sodium salt and a potassium salt, and an ammonium salt. From the viewpoint of cleaning performance, it is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight.

From the viewpoint of storage stability, the water content is preferably 10% by weight or less, more preferably 7% by weight or less, and even more preferably 5% by weight or less. The water content is determined according to JIS K 336.
2: 1998 Measured by the method specified by the weight loss method by heating.

The bulk density of the detergent composition is 500 to 1200 g.
/ L is preferred, 600 to 1000 g / L is more preferred, and 650 to 850 g / L is even more preferred. The bulk density is preferably 500 g / L or more from the viewpoint of economic efficiency, and 1200 g / L or less from the viewpoint of solubility. Incidentally, the bulk density is measured by a method specified by JIS K 3362.

The average particle size of the detergent composition is from 150 to
800 μm is preferred, 250 to 750 μm is more preferred, and 300 to 700 μm is even more preferred. It is preferably at least 150 μm from the viewpoint of preventing the formation of paste, and preferably at most 800 μm from the viewpoint of solubility. The average particle size is, for example, such that the sieve openings are 2000 μm, 1410 μm, 1000 μm, 710
μm, 500 μm, 350 μm, 250 μm, 177 μm
m and 125 μm sieves with openings of 125 μm
m, which can be obtained by classifying using a classifier consisting of a tray at the bottom and receiving particles passing through a sieve of m. The average particle diameter is a diameter of 50% by weight, and can be measured by using the above classifier. That is, after the classification operation, from the fine particles to the coarse particles, the weight frequency is sequentially integrated, and the opening of the first sieve at which the integrated weight frequency is 50% or more is set to a μm. When the opening is b μm, the integration of the weight frequency from the pan to the aμm sieve is c%, and the weight frequency on the aμm sieve is d%.
In this case, it can be determined according to the following equation (I).

[0044]

(Equation 3)

The detergent composition of the present invention can be obtained by a conventionally known production method. For example, (b), (b)
The detergent composition can be obtained by post-adding the components (c) and (d) and, if necessary, an enzyme and a fragrance. Further, when forming a granulated product containing the component (a), the component (d) is added, and the components (b) and (c) and, if necessary, an enzyme and a fragrance are added later to form a detergent composition. You can also get things. here,
In order to maintain the degree of neutralization of the component (d), it is important not to add the component (d) to an aqueous solution such as a slurry.

Further, in view of the fluidity and non-caking properties of the detergent composition, the surface may be modified with a surface coating agent. As the surface coating agent, for example, aluminosilicate,
Calcium silicate, silicon dioxide, bentonite, talc,
Clay, amorphous silica derivative, silicate compound such as crystalline silicate compound, metal soap, fine powder such as powdered surfactant, carboxymethyl cellulose, polyethylene glycol, sodium polyacrylate, copolymer of acrylic acid and maleic acid or the like Water-soluble polymers such as polycarboxylates such as salts; and fatty acids.

[0047]

Example [1] Preparation of powder detergent composition (a) (1-1) Preparation of spray-dried product A The components shown in Table 1 were mixed with water to prepare a detergent slurry having a solid content of 54% by weight ( Temperature 65 ° C). Note that LAS-N
a and sodium sulfate by-produced during the production of AS-Na, sodium sulfate (neutral anhydrous sodium sulfate)
Was adjusted by reducing the blending amount by the accompanying amount. This detergent slurry is spray-dried with a countercurrent spray-drying device to obtain a spray-dried product A.
I got The volatile matter (loss at 105 ° C. for 2 hours) of the obtained spray-dried product was 6%.

[0048]

[Table 1]

(Note) The symbols in Table 1 have the following meanings. LAS-Na; sodium alkylbenzene sulfonate having 10 to 13 carbon atoms in the alkyl group AS-Na; sodium alkyl sulfate having 12 to 16 carbon atoms in the alkyl group Nonionic surfactant; polyoxyethylene alkyl ether, An average of 8 moles of EO added to a higher alcohol containing 98% or more of a primary saturated alcohol having 12 carbon atoms in the alkyl group as a raw material. No. 1 sodium silicate; sodium silicate having a molar ratio of Na ₂ O / SiO ₂ of 2.15. AA / MA copolymer; acrylic acid / maleic acid copolymer sodium salt (monomer ratio 3: 7, Mw ≒ 5000)
0, degree of neutralization ≒ 80 mol%) ・ Tinopearl CBS-X: fluorescent dye, distyrylbiphenyl derivative (Ciba Specialty Chemicals Co., Ltd.)
-Tinopearl AMS-GX; fluorescent dye, bis- (triazinylamino) -stilbene-disulfonic acid derivative (manufactured by Ciba Specialty Chemicals Co., Ltd.).

(1-2) Preparation of Granular Detergent Composition (a) The spray-dried product obtained above was subjected to the following granulation operation. 74 parts by weight of the spray-dried product and 5 parts by weight of a powder zeolite (Toyobuilder (4A type, average particle size 3.5 μm); manufactured by Tosoh Corporation) together with a high-speed mixer (FS-GC-10; Fukae Kogyo Co., Ltd.) ), And the spray-dried product was crushed and stirred and granulated. At that time, 2.5 parts by weight of the nonionic surfactant was added by spraying. Before the end of granulation, 5 parts by weight of the above powdered zeolite was added. Next, the granulated material was sieved with a sieve having a mesh opening of 1.4 mm, and the coarse particles on the sieve were ground with a Fitz mill (manufactured by Hosokawa Micron Corporation) equipped with a punching metal screen having a pore size of 20 mm. The mixture was sieved with a sieve having a mesh size of 3 mm and mixed with the above-mentioned sieve. After 3 parts by weight of the above powdered zeolite was mixed with the V-blender with respect to the finished product, 0.5 part by weight of an enzyme granulation (Kannase 12T; manufactured by Novo) and a sodium percarbonate granulation (active oxygen content of 12%) were mixed. .4%, SPC-HG
D; manufactured by Mitsubishi Gas Chemical Company, Inc.), 4 parts by weight of the bleaching activator granules (A) (Note 1), 3 parts by weight, and 0.3 parts by weight of antifoaming agent granules (Note 2) The mixture was mixed with a V blender, and 0.2 part by weight of a fragrance was further added by spraying to obtain a granular detergent composition (a).
I got The resulting granular detergent composition has a bulk density of 770 g /
L, average particle diameter was 380 μm.

(Note 1) The bleaching activator granulated product (A) is prepared by the following method. 98.8 parts by weight of sodium decanoyloxybenzenecarboxylate powder and Emulgen KS-108 (5 moles of PO2 mole EO3 moles EO adduct of alcohol having 12 carbon atoms; manufactured by Kao Corporation) 5.2
Parts by weight and polyethylene glycol (K-PEG600
0; Kao Corporation) 22.1 parts by weight and succinic acid (20
3.9 parts by weight of a mesh pass product; manufactured by Kawasaki Kasei Kogyo Co., Ltd.) is charged into a Nauta mixer (NX-S type; manufactured by Hosokawa Micron Corp.) (charge amount 13 kg), jacket temperature 80 ° C., automatic rotation Mixing and raising the temperature at a number of 121 r / min and a revolving speed of 5.5 r / min.
When the mixture became, the mixture was extracted. Next, the obtained mixture was subjected to an extrusion granulator (pelleter double EXD-100).
(Powder, manufactured by Fuji Paudal Co., Ltd.) and extruded through a punching metal screen having a hole diameter of 0.7 mm to perform granulation.
The obtained extruded product is subjected to a vibration cooler (Vibro / flow dryer VDF / 6000 type; manufactured by Fuji Paudal Co., Ltd.)
After cooling, the granulator (knife cutter FL-200)
(Type). The obtained crushed material was classified using a classifier (Shouen vibrating sieve; manufactured by Tokuju Seisakusho Co., Ltd.), and the particle size was 350-1.
400 μm granules were obtained. This was designated as a bleach activator granulated product (A).

(Note 2) The defoamer granules were prepared by the following method. Dextrin (Pine Flow S-1)
0; 50 parts by weight of Matsutani Chemical Industry Co., Ltd.), 20 parts by weight of silicone (compound type FS anti-form DB100; manufactured by Dow Corning) and 25 parts of polyethylene glycol (Nissan polyethylene glycol # 6000; manufactured by NOF CORPORATION) 25 Parts by weight and 5 parts by weight of sodium sulfate (neutral anhydrous sodium sulfate; Shikoku Chemicals Co., Ltd.) are put into a Nauta mixer (NX-S type; manufactured by Hosokawa Micron Corp.) (mixing amount: 13 kg) and mixed, and jacket temperature is adjusted. The mixture was heated and mixed at 80 ° C., and the temperature of the powder was increased to 70 ° C. Next, the obtained mixture is extruded with an extrusion granulator (pelleter double EXD).
-100 type; manufactured by Fuji Paudal Co., Ltd.)
It was extruded and granulated through a punching metal screen of mm. The obtained extruded product is placed in a vibration cooler (vibro /
After cooling with a flow dryer VDF / 6000 type; manufactured by Fuji Paudal Co., Ltd., a granulator (knife cutter FL)
-200 type) to obtain granules.

[2] Partially neutralized organic chelating agent powder (I)
Preparation of partially neutralized organic chelating agent powder (I) is N, N-bis (carboxymethyl) -2-aminopentanedioic acid disodium salt having a degree of neutralization of 50%, and was prepared by the following method.

Glutamic acid, formalin and sodium cyanide were used as raw materials and N, N-bis (carboxymethyl) -2- was obtained by the method described in US Pat.
Aminopentanedioic acid tetrasodium salt was obtained. This is 36
The solution was neutralized with hydrochloric acid to convert a part of the carboxylate to the acid form, and the salt produced by electrodialysis was removed. Neutralization titration with perchloric acid confirmed that N, N-bis (carboxymethyl) -2-aminopentanedioic acid was a monosodium salt. Further, N, N-bis (carboxymethyl) -2-aminopentanedioic acid monosodium salt 2
100 g of a 40% aqueous sodium hydroxide solution was added to 85 g, and the mixture was freeze-dried after the reaction to obtain a dried product of disodium N, N-bis (carboxymethyl) -2-aminopentanedioate. The average degree of neutralization was identified by neutralization titration using perchloric acid and ¹³ C-NMR, and was confirmed to be 50%. The dried product is crushed in a mortar and partially neutralized organic chelating agent powder (I) by removing coarse particles with a sieve having an opening of 1 mm.
And

[3] Powder of fully neutralized organic chelating agent (II)
In the above [2], N, N-bis (carboxymethyl) -2-aminopentanedioic acid tetrasodium salt was powdered as it was to obtain a completely neutralized organic chelating agent powder (II).

Example 1 A granular detergent composition was prepared by adding 5 parts by weight of the partially neutralized organic chelating agent powder (I) to 95 parts by weight of the granular detergent composition (a) obtained above. This composition was evaluated for bleaching power and storage stability by the following methods. Table 2 shows the results. * Bleaching power <Evaluation contamination preparation of cloth> bilirubin _{(C 33 H 36 N 4 O} 6;
(MERK) 0.061 g in chloroform 100 ml
Dissolve in 0.4 ml of this solution is dropped onto a 10 cm × 10 cm cotton cloth # 2003 cloth per sheet and air-dried to obtain a bilirubin-contaminated cloth.

<Bleaching Rate Evaluation Method> Five 1 cm × 10 cm bilirubin-contaminated cloths prepared as described above were put into 1 L of an aqueous solution of the granular detergent composition, and 100 r / r was measured with a tergotometer.
Washed in minutes. The cleaning conditions were as follows: cleaning time: 10 minutes, composition concentration: 0.067%, water hardness: 4 ° DH, water temperature: 20
° C, rinse: 5 minutes in tap water. The bleaching power was measured by measuring the reflectance at 460 nm of the original cloth before and before and after the washing with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the bleaching rate (%) was determined by the following formula, and the average value of the measured values of the five sheets was measured. Was shown as bleaching power. Bleaching rate (%) = [(reflectance after washing-reflectance before washing)
/ (Reflectance of original cloth-reflectance before washing)] x 100 * Storage stability b Paper (No. 2: Toyo Roshi Kaisha, JIS P380)
12 equivalents), length 6cm, width 10cm, height 4c
Make a box-shaped top-open box. 120 g of the granular detergent composition to be evaluated is put in a container, stored at 30 ° C. and a humidity of 80% for 2 days, and the passage rate (solidification property) and the weight increase rate (hygroscopic property) of a 5 mm mesh screen are evaluated. .

Example 2 The bleaching activator granulated product (A) was replaced with the sodium decanoyloxybenzenecarboxylate powder of the bleaching activator granulated product (A) to be added to the granular detergent composition (a). B) was prepared and added to obtain a granular detergent composition (b). 5 parts by weight of the partially neutralized organic chelating agent powder (I) was added to 95 parts by weight of the granular detergent composition (b) to prepare a granular detergent composition. Table 2 shows the results of the same evaluation as in Example 1 for this composition.

Comparative Example 1 A granular detergent composition was prepared by adding 5 parts by weight of the completely neutralized organic chelating agent powder (II) in place of the partially neutralized organic chelating agent powder (I) to be added in Example 1. . Table 2 shows the results of the same evaluation as in Example 1 for this composition.

Comparative Example 2 The granular detergent composition (a) was used for evaluation without adding an organic chelating agent powder. Table 2 shows the results of the same evaluation as in Example 1 for this composition.

[0061]

[Table 2]

It can be seen that Example 1 is less likely to absorb moisture and harder to harden than Comparative Example 1. This is the effect of suppressing the hygroscopicity by using a partially neutralized organic chelating agent. Further, Example 1 has higher bleaching performance than Comparative Example 2. This is the effect of improving the bleaching performance by adding an organic chelating agent.

[4] Preparation of Powder Detergent Composition (b) In a jacketed mixing tank equipped with a stirrer, 539.
3 parts by weight were added, and the temperature was adjusted to 50 ° C. Sodium sulfate (neutral anhydrous sodium sulfate; Shikoku Chemical Industry Co., Ltd.) 1
29.6 parts by weight and 2.4 parts by weight of a fluorescent dye (Tinopearl CBS-X; manufactured by Ciba Specialty Chemicals Co., Ltd.) were added. After stirring for 10 minutes, 153.6 parts by weight of sodium carbonate (dense ash; manufactured by Central Glass Co., Ltd.) was added, and then a 40% by weight aqueous solution of sodium polyacrylate (described in Examples of Japanese Patent Publication No. 2-24283). Manufactured according to the method described in above, average molecular weight 10,000; manufactured by Kao Corporation) 19
After adding 5 parts by weight and further stirring for 10 minutes, 48 parts by weight of sodium chloride (yaki salt; manufactured by Nippon Seisho Co., Ltd.) and zeolite powder (Toyobuilder (4A type, average particle size = 3.5 μm))
m); 170.4 parts by weight (manufactured by Tosoh Corporation).
The mixture was further stirred for 30 minutes to prepare a slurry for spray drying.
The temperature of the resulting slurry for spray drying was 50 ° C. This slurry was spray-dried with a counter-current spray-drying apparatus equipped with a pressure spray nozzle, and volatile components (105 ° C., 2
(A reduction in time) was 3%, the bulk density was 520 g / L, the average particle size was 250 μm, and the loading capacity (Note 3) was 0.59 mL / g.

Next, 6 mol of EO was added on average to polyoxyethylene alkyl ether (Dovanol 23L, manufactured by Mitsubishi Chemical Corporation) mixed at 80 ° C.
6; manufactured by Kao Corporation) to 10 parts by weight of polyethylene glycol (average molecular weight: 8500, K-PEG6000;
A fatty acid equivalent to 1.2 parts by weight (manufactured by Kao Corporation) and 0.7 parts by weight as a fatty acid sodium [the composition of the alkyl group is C ₁₂ / C ₁₄ / C ₁₆ / C ₁₈ = 35/15/35/15] (Weight ratio), higher fatty acid, manufactured by Kao Corporation], alkylbenzenesulfonic acid equivalent to 12% by weight as sodium alkylbenzenesulfonic acid [composition of linear alkyl group: C
_{10 / C 11 / C 12 /} C 13 = 10/30/42/18 ( weight ratio), Neopelex GS; manufactured by Kao Corporation] and added fatty acids and neutralization equivalent of aqueous sodium hydroxide alkylbenzenesulfonate Thus, a water-containing surfactant composition having a water content of 11.5% by weight was prepared.

Next, 50 parts by weight of the above-mentioned support particles were charged into a Loedige mixer M20 type (manufactured by Matsuzaka Giken Co., Ltd.).
Main shaft (150r / min) and chopper (4000r / min)
Was started. 10 warm water of 80 ° C in the jacket
L / min flow rate. 27 parts by weight of the above-mentioned water-containing surfactant composition was added thereto for 2 minutes, followed by stirring for 4 minutes, and then pulverized (using a roller mill) to an average particle size of 8 μm (using SKS-6; Clariant Tokuyama). 10 parts by weight and the above powder zeolite 10
The surface coating treatment was performed for 2 minutes by adding parts by weight to obtain a detergent composition.

90 parts by weight of this detergent composition were mixed with 2 parts by weight of the above powdered zeolite in a V blender, and then 0.5 parts by weight of an enzyme granulation (Kannase 12T; manufactured by Novo) and sodium percarbonate were granulated. Product (effective oxygen content 12.4%,
4 parts by weight of SPC-HGD; manufactured by Mitsubishi Gas Chemical Co., Ltd., 3 parts by weight of the bleaching activator granules (B) (Note 4), and 0.3 part by weight of the defoaming agent granules in a V blender , And 0.2 part by weight of a fragrance is further added by spraying to obtain a granular detergent composition (b).
I got The resulting granular detergent composition (b) has a bulk density of 75
0 g / L, and the average particle size was 300 μm.

(Note 3) The measuring method of the carrying capacity is as follows. Approximately 5 cm inside diameter with a height of about 15 with stirring blades inside
cm in a cylindrical mixing tank, and put 350 g
While stirring at 30 ° C./min, polyoxyethylene alkyl ether (C ₁₂ / C ₁₄ = 6/4, average number of moles of added EO = 7.7, melting point 25 ° C.) was added dropwise at 30 ° C. at a rate of 10 mL / min and stirred. The change over time of the power is measured. The value obtained by dividing the input amount of the polyoxyethylene alkyl ether at the time when the stirring power becomes the highest by the weight (100 g) of the particle group is defined as the carrying capacity (mL / g) of the particle group.

(Note 4) The bleaching activator granules (B) are prepared by changing the sodium decanoyloxybenzenecarboxylate powder of the bleaching activator granules (A) to sodium lauroyloxybenzenesulfonate powder. did.

[5] Partially neutralized organic chelating agent powder (II
I) Partially neutralized organic chelating agent powder (III) has a degree of neutralization of 33%
N, N-bis (carboxymethyl) -2-aminopropanoic acid monosodium salt prepared by the following method. N, N-bis (carboxymethyl) -2-
Aminopropanoic acid trisodium salt (effective content 77%, Tr
(Ilon ES9964; manufactured by BASF) is dissolved in distilled water, and a neutralized equivalent amount of sulfuric acid is added and mixed. The mixture is concentrated by a rotary evaporator, and when the precipitation of salt starts, the concentrated liquid is left to stand on ice. The precipitated sodium sulfate was removed by filtration with a glass filter, and the filtrate was ethanol / water = 4.
/ 1 mixed solution. The collected liquid phase is passed through a rotary evaporator to distill off ethanol, and when crystals precipitate, they are removed by filtration. Ethanol is added to and mixed with the liquid phase after the distillation until turbidity does not disappear. The homogeneous gel is left on ice. The precipitate is collected by filtration.
At the time of recovery, wash with a mixed solution of ethanol / water = 4/1. Dry under reduced pressure to obtain a white powder. Elemental analysis and NMR analysis confirmed that the degree of neutralization was 33%. This dried product was removed with a sieve having an opening of 1 mm to remove coarse particles to obtain a partially neutralized organic chelating agent powder (III).

Example 3 A granular detergent composition was prepared by adding 5 parts by weight of the partially neutralized organic chelating agent powder (III) to 95 parts by weight of the granular detergent composition (b) obtained above. Table 3 shows the results of the same evaluation as in Example 1 for this composition.

Comparative Example 3 In Example 3, the partially neutralized organic chelating agent powder (II
Instead of I), 5 parts by weight of Trilon ES9964 powder (completely neutralized product) was added to prepare a granular detergent composition.
Table 3 shows the results of the same evaluation as in Example 1 for this composition.

Comparative Example 4 The granular detergent composition (c) was used for evaluation without adding an organic chelating agent powder. Table 3 shows the results of the same evaluation as in Example 1 for this composition.

[0073]

[Table 3]

It can be seen that Example 3 hardly absorbs moisture and hardens as compared with Comparative Example 3. This is the effect of suppressing the hygroscopicity by using a partially neutralized organic chelating agent. Further, the bleaching performance of Example 3 is higher than that of Comparative Example 4. This is the effect of improving the bleaching performance by adding an organic chelating agent.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C11D 3/395 C11D 3/395 17/06 17/06 (72) Inventor Hiroshi Nishimura 1334 Minato, Wakayama-shi, Wakayama Kao Corporation F-term in the laboratory (reference) 4H003 AB03 AB19 AB27 AC08 BA09 DA01 EA12 EA15 EA16 EA28 EB09 EB19 EB22 EB32 EB36 EE05 FA07 FA41 FA43

Claims (4)

[Claims] (1) 5 to 50% by weight of a surfactant,
(B) Particles releasing hydrogen peroxide in an aqueous solution 0.1 to 1
0% by weight, (c) 0.05 to 5% by weight of a bleaching activator, and (d) 3 to 5 carboxyl groups per molecule, having a molecular weight of 600 or less and an average degree of neutralization of 20 to 70%. And a detergent composition comprising 0.5 to 30% by weight of a chelating agent comprising a compound having a chelate stability constant of 6 to 13 with Ca ²⁺ . 2. The detergent composition according to claim 1, wherein (b) is a carbonate / hydrogen peroxide adduct and / or a borate / hydrogen peroxide adduct. 3. The detergent composition according to claim 1, wherein (c) is selected from compounds represented by the following general formulas (1) to (4). Embedded image [Wherein, R ₁ represents an alkyl group having 4 to 13 carbon atoms, R ₂ represents an alkyl group having 5 to 13 carbon atoms, and M represents a hydrogen atom or an alkali metal, an alkaline earth metal, ammonium or alkanolamine. [Chemical formula 2] [Wherein, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ , and R ₁₀ are each independently an alkyl group or hydroxyalkyl group having 1 to 5 carbon atoms, and R ₈ is 2 to 10 alkylene groups, and X ⁻ represents an anion. ] 4. The detergent composition according to claim 1, wherein (d) comprises a compound represented by the following general formula (5). Embedded image Wherein R ₁₁ is — (CH ₂ ) _n —A, wherein A is a hydrogen atom,
A hydroxyl group or COOM ₁ , M ₁ is a hydrogen atom, an alkali metal or ammonium, and n represents 0 to 3. ]