JPH10330787A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-density detergent compsn. which has a detergency improved from the viewpoint of the recipe of main detergent ingredients by compounding an anionic surfactant, a cationic surfactant of a quaternary ammonium salt type, and an org. builder of an aminopolycarboxylic acid type. SOLUTION: The anionic surfactant (A) comprises at lest one surfactant selected from among sulfuric ester salts, alkanesulfonates, alkylbenzenesulfonates, etc., of higher alcohols and is used in an amt. of 20-50 wt.% of the compsn. The cationic surfactant of a quaternary ammonium salt type (B) comprises at least one surfactant selected from among alkyltrimethylammonium salts, quaternary salts of polyoxyethylenealkylamines, etc., and is compounded in a molar ratio to ingredient A of (1/100)-(20/100). The builder of an aminocarboxylic acid type (C) is resented by the formula (wherein M is H, Na, K, or NH4 ; A is H or OH; R is (CH2 )n -B; B is OH or COOH; and (n) is 0-3), has a Ca chelate stability constant of 6.0 or higher, and is compounded in an amt. of 3-40 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a detergent composition having high detergency. More specifically, a surfactant having a specific mixing molar ratio of an anionic surfactant and a cationic surfactant is used, and an alkali agent, an inorganic builder, an organic builder having a Ca chelate stability constant of 6.0 or more are blended with the surfactant. Detergent detergent composition.

[0002]

2. Description of the Related Art A detergent for clothing is a surfactant which solubilizes stains, dissolves and disperses from fibers into a washing liquid, an alkali agent which promotes decomposition and solubilization (emulsification) of stains, and the ability of a surfactant. It is basically composed of a sequestering agent or the like that captures calcium, magnesium, etc., in the washing liquid, which lowers the water content. Among these components, those that do not exhibit cleaning performance by themselves, but which improve the cleaning power by being combined with a surfactant or the like, are generally called detergent builders. Among the builders, a component that blocks metal ions (hardness component) contained in water such as calcium is called a hardness component blocking agent. In order to more effectively exhibit the performance of a surfactant, it is necessary to prevent the formation of a calcium salt or a magnesium salt of the surfactant, and therefore, the function of the hardness component blocking agent is very important.

[0003] The hardness component blocking agent is divided into inorganic builders such as zeolite (crystalline aluminosilicate) and tripolyphosphate, and organic builders such as EDTA (ethylenediaminetetraacetate) and NTA (nitrotriacetate). Can be Since the inorganic builder is inexpensive, a considerable amount is added to the detergent for the purpose of sequestering metal ions such as calcium in the washing liquid and for improving the powder properties of the detergent.

[0004] However, since the ability to sequester metal ions such as calcium is not sufficient, higher fatty acids contained in sebum dirt combine with residual calcium and magnesium ions in the washing liquid to form insoluble metal salts. When this is generated, the washing property of sebum dirt decreases. In order to replace these salts once formed with salts such as sodium and potassium, the value of the Ca chelate stability constant is required to be at least 6.0 or more, and the above inorganic builder alone is not sufficient. Meanwhile, organic builders EDTA and NTA C
a The value of the chelate stability constant is 6.0 or more in the case of alkali, and if a sufficient amount of organic builder is used, it is possible to sequester metal ions in the washing liquid or to use sodium such as calcium salt such as oleic acid in the soil component. Since the replacement is performed, the cleaning property is remarkably improved. However, although sufficient in terms of cleaning performance, there are restrictions on safety, biodegradability, cost, etc. in order to be actually incorporated into detergents. Builders are being actively researched.

[0005] Surfactants to be added to the detergent are commercially available as anionic solely, anionic-based one containing a small amount of nonionic, or nonionic-based one containing an appropriate amount of anionic. .

Further, at present, the densification and miniaturization of detergents are proceeding in accordance with market demands such as resource saving, labor saving, and reduction of transportation costs.
The role of alkaline agents, builders, etc. is becoming increasingly important. In particular, advances in surfactants and builders that further improve detergency are expected.

[0007]

Since the absolute value of the amount used in a high-density detergent is limited, a surfactant, an alkali agent,
All of the builders need to perform in smaller amounts. Under such circumstances, an object of the present invention is to provide a high-density detergent with improved detergency in terms of the composition of these main detergent components.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, have found that a mixture of an anionic surfactant and a cationic surfactant having a specific mixture molar ratio and a Ca chelate stable agent. The inventor has found that the incorporation of an organic builder having a degree constant of 6.0 or more at a specific ratio significantly improves the detergency, thereby completing the present invention.

That is, the present invention relates to (a) 20 to 50% by weight of an anionic surfactant, (b) a quaternary ammonium salt type cationic surfactant having an alkyl group having 6 to 14 carbon atoms, and (c) a stability constant of Ca chelate. Is an aminopolycarboxylic acid type organic builder represented by the following general formula (I) having a value of 6.0 or more: 3 to 40% by weight

[0010]

Embedded image

Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is — (CH ₂ ) _n —B, B is OH or COOH, and n is 0-3. is there. ]
The molar ratio of (b) / (a) is (b) / (a) = 1/100
２０20/100. Hereinafter, the components (a) to (e) of the present invention will be described.

[Component (a)] Examples of the anionic surfactant include a sulfate of a higher alcohol, a sulfate of a polyoxyethylene alkyl ether, an alkane sulfonate (SAS), an α-olefin sulfonate and an α-olefin sulfonate.
-One or more anionic surfactants selected from sulfo fatty acid alkyl ester salts and alkyl benzene sulfonates are preferably used. As the sulfate salt of a higher alcohol, the alkyl group has 8 to 1 carbon atoms.
8, especially 10 to 14 sulfuric ester salts of primary and secondary higher alcohols. As the sulfate ester salt of polyoxyethylene alkyl ether, those having an average ethylene oxide addition mole number of 0.5 to 3 and an alkyl group portion having 8 to 18 carbon atoms are preferable. The alkyl group portion of the alkylbenzene sulfonate has 8 to 1 carbon atoms.
8, particularly preferably 8 to 16. 20 to 50% by weight, preferably 25 to 40% by weight, is blended with the anionic surfactant (a) in the composition.

[Component (b)] The component (b) of the present invention is a quaternary ammonium salt type cationic surfactant having an alkyl group having 6 to 14 carbon atoms. As this type of surfactant, the following general formula

[0014]

Embedded image

Wherein R is an alkyl or alkenyl group of an alkyl group having 6 to 14 carbon atoms or an alkyl or alkenyl group having 6 to 14 carbon atoms having an oxyethylene chain of 1 to 6; , X are halogen elements such as chlorine and bromine, and counter ions such as methyl sulfate and ethyl sulfate. Represented by an alkyl mono- or di-polyoxyethylene mono- or dimethylammonium salt, an alkyltrimethylammonium salt, an alkylbenzylammonium salt,
And quaternized salts of polyoxyethylene alkylamine. In particular, in the present invention, as the component (b), alkyl (C ₆ -C ₁₄ ) trimethylammonium salt, quaternized salt of polyoxyethylene (n: 1 to 6) alkyl (C ₆ -C ₁₄ ) amine and alkyl (C 6 ₆ -C ₁₄₎ 1, two or more cationic surfactants selected from benzyl dimethyl ammonium salts are preferred. The component (b) is
The molar ratio with the component (a) is (b) / (a) = 1 / 100-
20/100, preferably 2.5 / 100 to 7.5 / 1
It is blended in the composition within the range of 00. The cleaning performance improves as the value of (b) / (a) increases, but the effect of preventing re-contamination decreases. In this range of molar ratio, the balance between the cleaning effect and the effect of preventing re-contamination is optimal, and the cleaning effect is excellent.

[Component (c)] The component (c) of the present invention comprises:
It is an organic builder having a Ca chelate stability constant of 6.0 or more. The role of the "builder" in the present invention is to capture hardness ion components such as calcium and magnesium in the washing liquid and replace the salt of the higher fatty acid hardness ion component in the soil component with ions such as sodium, potassium and ammonium. What you can do. C for capturing the hardness component
a The larger the trapping amount, the better. The amount of Ca captured is 200
(CaCO ₃ mg / g) or more, more preferably 300 (CaCO ₃ mg / g) or more. The capture of the hardness component in the washing liquid is particularly necessary in order to sufficiently exert the function of the surfactant. In order to replace the salt of the hardness ion component of higher fatty acids with sodium or the like, the builder needs C
a The chelate stability constant is 6.0 or more, preferably 6.5.
It is necessary to have the above values. When a builder having a Ca chelate stability constant of 6.0 or less is used, the higher fatty acid in the dirt component converted into a salt of the hardness ion component is not easily replaced with a sodium salt or the like. Also, it is difficult to remove the hardness component from the washing liquid to a certain degree or more.

In the present invention, the organic builder as the component (c) meets the purpose if the Ca chelate stability constant is 6.0 or more. Particularly, the compound of the general formula (I), among which the following formula (I) The aminopolycarboxylic acids represented by I) -1 to (I) -4 have good biodegradability, have chelating power,
Suitable as the organic builder of the present invention.

[0018]

Embedded image

Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is-(CH ₂ ) _n -B, B is OH or COOH, and n is 0-3. is there. ]

[0020]

Embedded image

It is preferable to mix the component (c) in as large an amount as possible from the viewpoints of capturing the hardness ion component in the washing liquid and replacing the hardness ion component of the higher fatty acid in the soil with sodium or the like. Taking into account the amount and price of other components necessary for developing cleaning performance, 3-40% by weight,
Preferably it is 6 to 30% by weight.

In the present invention, the Ca chelate stability constant is determined by the following method. 0.1 mol / l NH ₄ Cl—NH ₄ OH as 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. Calcium 5.36 × 10 ^-2 mol / liter of chloride solution, a chelating agent sample 5.36 × 10 ^-4 mol / l solution is prepared.
1 ml of calcium chloride solution is added to 100 ml of the chelating agent sample solution, and the mixture is stirred for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. The chelating agent is C
Assuming that a chelate complex is formed at a ^ratio of 1: 1 with a ²⁺ , the Ca chelate stability constant is determined from the following equation.

[0023]

(Equation 1)

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In addition to the above components (a) to (c), the following components can be added to the detergent composition of the present invention.

<Alkali agent> Examples of the alkali agent include inorganic alkali metal salts. Specifically, sodium carbonate, potassium carbonate, sodium silicate [(Na ₂ O) _m (Si
O ₂ ) _n , where m is 1 to 3 and n is 1 to 5], sodium bicarbonate, potassium bicarbonate, sodium sulfite, potassium sulfite, sodium sesquicarbonate, potassium sesquicarbonate, crystalline silicate, etc. It is. In particular, it is preferable to mix the crystalline silicate as a part or all of the alkali agent.

The crystalline silicate used in the present invention has a temperature of 20 ° C.
PH when 0.1% by weight is dispersed in deionized water
Is 11 or more, and p per 1 liter of the dispersion is p
It is excellent in alkali ability that requires 5 ml or more of 0.1N HCl aqueous solution to make H equal to 10, and is distinguished from crystalline aluminosilicate.

Particularly preferred as crystalline silicates are those having the following composition: _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (i) wherein, M is Group Ia elements of the periodic table (particularly preferably K and / Or Na), and Me is an element of group IIa of the periodic table, II
One or a combination of two or more selected from group b elements, group IIIa elements, group IVa elements or group VIII elements (preferably M
g / Ca), y / x = 0.5-2.6, z / x = 0.01-
0.9, w = 0 to 20, and n / m = 0.5 to 2.0. The production method of the crystalline silicate represented by the general formula (i) can be referred to JP-A-7-89712.

Further, a crystalline silicate having the following composition can also be suitably used. _{M 2 O · x '(SiO} 2) · y' (H 2 O) (ii) wherein, M represents an alkali metal (particularly preferably K and / or Na), x '= 1.5~2.6, y '= 0 to 20 (particularly preferably substantially 0). The crystalline silicate of the general formula (ii) is disclosed in JP-A-60-227895, Phys. Chem. Glasses. 7, 127-138 (1966), Z. Kristall
ogr., 129, 396-404 (1969). In addition, a powdery or granular product is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ).

The alkaline agent is 5 to 40% by weight in the composition,
Preferably, the content is 10 to 30% by weight. The blending of the alkaline agent promotes solubilization of proteins in soil, decomposition and emulsification of fats and oils components, and improves the cleaning effect. (I), (i
i) a crystalline silicate of the formula
When it is contained in an amount of 10 to 10% by weight, the alkali buffering ability and the ability to capture the hardness component are increased, and the cleaning effect is also improved.

<Inorganic builder> Examples of the inorganic builder used in the present invention include aluminosilicate (such as zeolite) and polyphosphate. That is, the following (1) and (2) can be used.

(1) Aluminosilicate Either crystalline or amorphous aluminosilicate can be used. However, crystalline aluminosilicate (zeolite) has a higher ability to exchange calcium and the like, and therefore, is preferably used. Zeolite is mainly used for the purpose.

Zeolite is represented by the following general formula.

A '(M ₂ O) .Al ₂ O ₃ .b' (SiO ₂ ) .w (H ₂ O) (where M is an alkali metal atom, and a ', b', w are Represents a molar ratio, generally 0.7 ≦ a ′ ≦ 5, 0.7 ≦ b ′ <6,
w is any positive number. Among them, those represented by the following formula are preferable.

M ₂ O · Al ₂ O ₃ · b ′ (SiO ₂ ) · w (H ₂ O) b ′ is 1.8 to 3.0, and w is 1 to 6.

As the zeolite, a synthetic zeolite having an average primary particle size of 0.1 to 10 μm typified by A-type, X-type and P-type zeolites is preferably used.

(2) Polyphosphate (Condensed Phosphate) Polyphosphates such as orthophosphate, metaphosphate, pyrophosphate, tripolyphosphate, and hexametaphosphate can be used in the present invention. H, N
a and K are common.

The alkaline agent is contained in the composition in an amount of 5 to 40% by weight,
Preferably, the content is 15 to 30% by weight. In particular, (1)
And (2) may be used alone or as a mixture.

<Enzyme> Enzymes (enzymes which essentially perform an enzymatic action during the washing step) can be classified into hydrolases, oxidoreductases, lyases, transferases, and isomerases by classifying them based on their reactivity. But any of them can be applied to the present invention.
Particularly preferred are proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases.

In the present invention, the enzyme can be incorporated in the composition in an amount generally known.

<Fluorescent Dyes> As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, One or more of a ((styrylphenyl) naphthothiazole derivative, a 4,4'-bis (triazol-2-yl) stilbene derivative, and a bis (triazinylamino) stilbene disulfonic acid derivative in a composition, ~ 2
Wt%, for example, Whitex SA
Commercially available products such as (Sumitomo Chemical Co., Ltd.) and Tinopearl CBS (Ciba-Geigy) can be used.

<Other Components> In addition, organic sequestering agents such as ethylenediaminetetraacetic acid (EDTA) and citrate, carboxylic acids such as polyacrylic acid, a copolymer of acrylic acid and maleic acid, and carboxymethyl cellulose. Polymers, extenders such as sodium sulfate, dispersants or color transfer inhibitors (PVP) such as polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP) and polyvinyl alcohol (PVA), bleaching agents such as sodium percarbonate, No. 316700 and bleach activators such as tetraacetylethylenediamine (TAED), enzyme stabilizers such as boron compounds and sodium sulfite, defoamers such as silicone / silica, antioxidants, bluing agents and fragrances Conventionally known components such as can be blended in a known blending amount. .

The method for producing the detergent composition of the present invention is not particularly limited, and a conventionally known method can be used. Preferably, the detergent has a bulk density of 0.6 to 1.2 g / cm ^{3 and} a high bulk density. Examples of the method for increasing the bulk density include a method of spraying a nonionic surfactant on spray-dried particles to increase the density, and a method of increasing the density while directly absorbing nonions into the powder component including the oil absorbing carrier. JP-A-61-69897, JP-A-61-69899, JP-A-61-69900, JP-A-2-222498, JP-A-2-222499, The methods described in JP-A-3-33199, JP-A-5-86400, and JP-A-5-209200 can be referred to. When a crystalline aluminosilicate is blended as the aluminosilicate, a small amount thereof may be added during granulation or immediately before the completion of granulation, since it can be used for surface modification of the granulated material. When a crystalline silicate is blended, the crystalline silicate is preferably added at the time of increasing the bulk density or by dry blending. In addition, when blending an alkali metal carbonate,
It may be added during granulation or in the dry blend.

[0043]

According to the present invention, a mixture of an anionic surfactant and a specific quaternary ammonium salt type cationic surfactant in a limited molar ratio as the surfactant [component (a), component (b)] By using a specific ratio of an organic builder [component (c)] having a Ca chelate stability constant of 6.0 or more, a detergent composition excellent in detergency and prevention of recontamination can be obtained.

[0044]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (1) Preparation of High-Density Granular Detergent Composition Product 1 of the present invention shown in Table 1 was prepared by the following procedure. (I) -1
1.0 kg, zeolite 1.0 kg, AS 3.0 k
g, C ₈ -4 quaternary salt 0.1kg, AM0.4kg, 2 No. sodium silicate 1.0 kg, sodium carbonate 1.5 kg,
Fluorescent dye (4,4'-bis- (2-sulfostyryl)-
A water slurry having a solid content of 60% by weight was prepared from 0.05 kg of biphenyl salt) and sodium sulfate used for the balance, and this was spray-dried. The obtained particles are put into a high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and further, zeolite 0.25 k
g, 0.5 kg of crystalline silicate (i) was added, and 0.1 kg of PEG heated to 70 ° C. was gradually dropped into the mixture while mixing to perform granulation. 0.5k 30 seconds before the end of granulation
g of zeolite was added. The resulting granulated particles were dry-mixed with 0.25 kg of the above and 0.1 kg of an enzyme to prepare a high-density granular detergent composition (average particle size of 4).
40 μm, bulk density 790 g / l). For other products of the present invention and comparative products, high-density granular detergent compositions were prepared according to the above-mentioned schemes, with the respective mixing ratios.

(2) Performance Evaluation Using the samples of the product of the present invention and the comparative product prepared by the above method, the re-contamination prevention performance and the cleaning performance were evaluated by the following methods. The results are shown in Tables 1 to 4.

Evaluation method of recontamination prevention performance After dissolving 2.5 g of the detergent composition in 1 liter of tap water,
0.20 g of carbon black was added, and ultrasonic waves were
Irradiation for 1 minute, the carbon black was uniformly dispersed.
This test bath is used as a Terg-o-Tometer.
After transfer to a washing bath, clean raw cloth (10 cm × 1
0cm) and add 1 at 20 ° C with a tergotometer.
Stirred for 0 minutes. As soon as the turgotometer stopped rotating, the sample cup was immediately removed, the unprocessed cloth was taken out, and the rinsing was performed in running water for approximately a certain time in a washing tub. The unprocessed cloth was dehydrated in a dehydration tub of a washing machine, and was press-dried (inserted with a pressing pad and dried at 130 ° C. for about 30 to 40 seconds). The reflectance of the clean unprocessed cloth and the contaminated unprocessed cloth was measured, and the re-contamination prevention rate was determined by the following equation. Re-contamination prevention rate (%) = R (s) / R (o) × 100 where R (s) = reflectance of contaminated raw cloth R (o) = reflectance of clean raw cloth Yes, the re-staining prevention rate indicated the average value of six stained raw cloths.

Evaluation Method of Cleaning Performance (Preparation of Artificial Stained Cloth) An artificially contaminated liquid having the following composition was adhered to a cloth to prepare an artificially contaminated liquid. The artificial contaminant was attached to the cloth by printing the artificial contaminant on a cotton cloth using a gravure roll coater. The step of preparing the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth was performed at a gravure roll cell capacity of 58 cm ³ / cm ² , an application speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. The cloth used was a cotton cloth 2003 (manufactured by Tanito Shoten).

[Composition of artificial contaminated liquid] Lauric acid 0.44% by weight Myristic acid 3.09% by weight 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57 Weight% oleic acid 7.75 weight% triolein 13.06 weight% n-hexadecyl palmitate 2.18 weight% squalene 6.53 weight% egg white lecithin liquid crystal 1.94 weight% Kanuma red soil 8.11 weight% carbon black 0.01% by weight tap water balance (Washing conditions and evaluation method) Five 1 cm × 10 cm artificially contaminated cloths prepared as described above were placed in 1 liter of an aqueous cleaning agent solution for evaluation, and washed with a tergotometer at 100 rpm. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Washing agent concentration 0.067% by weight Water hardness 4 ° DH Water temperature 20 ° C. Rinse with tap water 5 minutes Washing power is 550n of original cloth before and after cleaning
The reflectance at m was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), the cleaning rate (%) was determined by the following equation, and the measured average value of the five sheets was shown as the cleaning power.

[0050]

(Equation 2)

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

AS: Sulfuric acid ester sodium salt of higher alcohol (C ₁₂ ) LAS: Linear alkyl (C ₁₂ ) benzenesulfonic acid sodium salt α-SFE: α-sulfo fatty acid (C ₁₂ ) methyl ester sodium salt C ₈ -4 quaternary salt: octyl trimethylammonium chloride · C ₁₀ -4 quaternary salt: decyl trimethyl ammonium chloride · C ₁₂ -4 quaternary salt: bank sill trimethylammonium chloride · C _12B -4 quaternary salt: bank sill benzyl dimethyl ammonium chloride · C _12E -4 quaternary salt: bank sill dimethyl polyoxyethylene chloride crystalline silicate _{(i): M 2 O ·} 1.8SiO 2 · 0.0
2M'0 (where M: Na, K, K / Na = 0.0
3, M ′ = Ca, Mg, Mg / Ca = 0.01), ion exchange capacity 224 CaCO ₃ mg / g, average particle size 12
μm crystalline silicate (ii): M ₂ O · 2SiO ₂ , ion exchange capacity 224 CaCO ₃ mg / g, average particle diameter 30 μm,
Trade name SKS (manufactured by Hoechst-Tokuyama) ・ Zeolite: crystalline aluminosilicate, M ₂ O ・ A
l ₂ O ₃ .2SiO ₂ .2H ₂ O, average particle diameter 2 μm, ion exchange capacity 290 CaCO ₃ mg / g. (I) -1: aminopolycarboxylic acid sodium salt (Ca) represented by the formula (I) -1 (I) -2: Aminopolycarboxylic acid sodium salt represented by the formula (I) -2 (Ca chelate stability constant 6.0). (I) -3: Formula (I) Aminopolycarboxylic acid sodium salt represented by I) -3 (Ca chelate stability constant: 8.0) · (I) -4: Aminopolycarboxylic acid sodium salt represented by formula (I) -4 (Ca chelate) Stability constant 6.5) AM: sodium salt of maleic acid acrylate (7/3 molar ratio) copolymer, average molecular weight 70000 PA: sodium polyacrylate, average molecular weight 80
00 • PEG: polyethylene glycol having an average molecular weight of 7,000 • Enzyme: protease [Savinase 12.0T type]
e W (Novo Nordisk)], lipase [Lipolase 100T (Novo Nordisk)], cellulase [KAC500G (Kao Corporation)], and amylase [Termamyl 60T (Novo Nordisk)] in 2:
1: 1: 1 mixture: Common component: 0.5% by weight of fluorescent component and Glauber's salt, and the total amount of Glauber's salt was adjusted to 100% by weight.

AE: polyoxyethylene dodecyl ether (HLB13.1)

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 29, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is — (CH ₂ ) _n —B, B is OH or CO
OM, n is 0-3. (B) / (a)
Is (b) / (a) = 1/100 to 20/100
A detergent composition.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is-(CH ₂ ) _n -B, B is OH or COOM, and n is 0-3. is there. ]
The molar ratio of (b) / (a) is (b) / (a) = 1/100
２０20/100. Hereinafter, the components (a) to (e) of the present invention will be described.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is — (CH ₂ ) _n —B, B is OH or COOM, n is 0-3. is there. ]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/62 C11D 1/62 3/33 3/33

Claims (4)

[Claims] (A) 20 to 50% by weight of an anionic surfactant; (b) quaternary ammonium salt type cationic surfactant having an alkyl group having 6 to 14 carbon atoms; and (c) Ca chelate stability constant of 6. Aminopolycarboxylic acid type organic builder represented by the following general formula (I) having a value of 0 or more: 3 to 40% by weight Wherein M is selected from H, Na, K and NH ₄ , A is H or OH, R is — (CH ₂ ) _n —B, B is OH or CO
OH, n is 0-3. (B) / (a)
Is (b) / (a) = 1/100 to 20/100
A detergent composition. 2. The detergent composition according to claim 1, wherein the organic builder of (c) is at least one selected from the following formulas (1) -1 to (1) -4. Embedded image 3. The quaternary ammonium salt type cationic surfactant (b) is an alkyl (C ₆ -C ₁₄ ) trimethylammonium salt, a polyoxyethylene (n: 1-6) alkyl (C ₆ -C ₁₄ ) Amine quaternary salts and alkyl (C ₆
-C ₁₄₎ is one or more cationic surfactants selected from benzyl dimethyl ammonium salt according to claim 1
Or the detergent composition according to 2. 4. The method according to claim 1, wherein the molar ratio of (b) / (a) is (b) /
The detergent composition according to any one of claims 1 to 3, wherein (a) is 2.5 / 100 to 7.5 / 100.