JPH10102092A - Granular detergent composition having high density - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of exhibiting an excellent detergency and solubility even when washed at a low water temperature by compounding a system containing a surfactant as a main washing base with a specific aminopolycarboxylic acid. SOLUTION: This composition comprises (A) 0.1-30wt.% aminopolycarboxylic acid compound of the formula [R<1> and R<2> are each H or CH3 or at least either one of R<1> and R<2> is CH3 ; R<3> is CH2 COOM (M is H, Na, K or NH4 ), CH(OH) COOM, CH2 CH.COOM or CH2 0H], (B) 10-50wt.% surfactant and (C) 5-30wt.% crystalline aluminosilicate and has 0.6-1.2g/ml bulk density. A synthetic zeolite having 0.1-10μm average primary particle diameter, e.g. A type, X type or P type zeolite is preferably used as the component C. The composition can readily be dissolved in cold water and is excellent in detergency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to high-density detergent compositions. More specifically, the present invention relates to a high-density granular detergent composition which is easily dissolved in cold water and has excellent detergency.

[0002]

2. Description of the Related Art A detergent for clothing is a surfactant for solubilizing stains and dissolving and dispersing the stains into washing liquid from fibers, an alkali agent for promoting the decomposition and solubilization of the stains, and a polymer compound for dispersing the stains. It basically comprises a sequestering agent or the like for removing calcium, magnesium or the like, which lowers the ability of the surfactant, from the washing liquid.

[0003] Of these components, those which do not exhibit cleaning performance by themselves, but which are intended to improve the detergency by combining with a surfactant or the like, are generally called detergent builders. Among these detergent builders, the above-mentioned sequestering agent is a substance for more effectively expressing the performance of the surfactant, and is one of extremely important detergent builders.

In the past, phosphorus compounds such as sodium tripolyphosphate were blended in clothing detergents as sequestering agents, but phosphorus compounds are considered as one of the causes of eutrophication in lakes and swamps. The detergent industry has been developing phosphate builder-free detergents. At present, crystalline sodium aluminosilicate having a specific structure (referred to as zeolite in the art) has no problems in phosphate-type builders and has been stable in price in recent years. It is the main component of the agent.

[0005] Since the late 1980's, laundry detergents have undergone a transformation, and so-called compact detergents, which have a high bulk density and a small capacity when used, have become the mainstream. However, since the detergent particles of the compact detergent are more compact than conventional detergent particles, solubility becomes a problem. Since zeolite is itself water-insoluble, it may cause water-insoluble substances to be generated when washing with a compact detergent at a low water temperature. In addition, the mechanism of sequestering the hardness component of zeolite is ion exchange, and the exchange rate is kinetic-limited by the diffusion of exchanged ions in the zeolite. Therefore, it takes a long time for ion exchange at a low water temperature, and the detergency at a low temperature is insufficient. In particular, it takes a very long time to exchange large Mg ions in the hydrated shell. With respect to this problem, the present applicant has attempted to solve the problem by making various efforts in the composition and manufacturing method of the compact detergent. Excellent detergent builders are still being developed.

[0006] On the other hand, zeolite is a water-insoluble detergent builder, and organic builders such as polycarboxylic acid polymers are known as water-soluble detergent builders. Specific examples include a polymer of a vinyl compound having a carboxyl group. For example, a polyacrylate having a molecular weight in the oligomer region, a salt of an acrylic acid / maleic acid copolymer, a salt of an olein / maleic acid copolymer, or the like. Since these polycarboxylic acid polymers are water-soluble, they are effective in sequestering polyvalent cations at low water temperatures, and are expected to improve the detergency of detergents at low temperatures.

[0007]

However, the polycarboxylic acid-based polymer tends to thicken the detergent paste, and thus has a problem of lowering the solubility of the detergent. Therefore, even a system containing these polycarboxylic acid polymer-based builders still cannot provide sufficient detergency under low-temperature conditions. Under such circumstances, an object of the present invention is to find a builder component which exhibits excellent detergency even when washed under low water temperature conditions and does not impair the solubility, and an excellent high-density detergent composition containing the same. It is to provide.

[0008]

Means for Solving the Problems As a result of various studies, the present inventors have found that a system using a surfactant as a main cleaning base has the following properties.
The inventor has found that by adding the aminopolycarboxylic acid compound represented by the formula (I), a detergent composition having excellent low-temperature detergency can be obtained, thereby completing the present invention.

That is, the present invention relates to (a) an aminopolycarboxylic acid compound represented by the following general formula (I): 0.1 to 30% by weight;

[0010]

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(B) a high-density granular detergent composition containing 10 to 50% by weight of a surfactant, (c) 5 to 30% by weight of a crystalline aluminosilicate and having a bulk density of 0.6 to 1.2 g / ml. To provide. Hereinafter, the high-density granular detergent composition of the present invention will be described in detail.

(A) Organic builder The organic builder used in the present invention is represented by the general formula (I), wherein M (counter ion) in the general formula (I) is hydrogen, sodium, potassium, ammonium Is common. The partially neutralized one has the highest sequestering ability of metal ions and has a high detergency improving effect, but the completely neutralized one also shows a sufficient detergency improving effect.

In the present invention, the organic builder of the component (a) is incorporated in the composition in an amount of 0.1 to 30% by weight, preferably 2 to 20% by weight. When the amount of the component (a) is within this range, good detergency can be obtained even under low temperature conditions. As the aminopolycarboxylic acid compound represented by the general formula (I), the following formula (IV)
To (XI) are preferred.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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(B) Surfactant The high-density granular detergent composition of the present invention contains 10 to 50 surfactants.
%, Preferably 15 to 40% by weight. As the surfactant, an anionic surfactant, a nonionic surfactant,
Amphoteric surfactants and cationic surfactants are used,
Preferred are anionic surfactants and nonionic surfactants.

[0023] The anionic surfactants include those having 10 to 10 carbon atoms.
Sulfate of 18 linear or branched primary or secondary alcohols, sulfate of ethoxylated alcohol having 8 to 20 carbon atoms, alkylbenzene sulfonate, paraffin sulfonate, α-olefinsulfonic acid Salts, α-sulfofatty acid salts and α-sulfofatty acid alkyl ester salts are preferred.

As the nonionic surfactant, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, and polyoxyethylene polyoxypropylene block polymer are preferable. . In particular, as a nonionic surfactant, an alkylene oxide such as ethylene oxide or propylene oxide is added to a linear or branched primary or secondary alcohol having 10 to 18 carbon atoms, and HL is used.
B value (calculated by the Griffin method) of 10.5-15.0, preferably
Polyoxyalkylene alkyl ethers adjusted to 11.0 to 14.5 are preferred.

The anionic surfactant and the nonionic surfactant are used in an amount of 0.5 to 25 parts by weight, preferably 2.0 to 9.0 parts by weight, more preferably 4.0 to 25 parts by weight, based on 100 parts by weight of the anionic surfactant. It is preferable to use them together in a ratio of up to 7.0 parts by weight, and by using this ratio, the detergency for inorganic particles such as mud stains is improved.

(C) Crystalline aluminosilicate The crystalline aluminosilicate used in the present invention is generally called zeolite, and has the following formula a ′ (M ₂ O) · Al ₂ O ₃ .b ′ _{(SiO 2) · w (H} 2 O) (iii) wherein, M represents an alkali metal atom, a ', b', w represent mole ratios of each component, in general, 0.7 ≦ a '≦ 1.5 , 0.8 ≤ b '<
6, w is any positive number. ], And
Among them, the following general formula (iv): Na ₂ O.Al ₂ O ₃ .n (SiO ₂ ) .w (H ₂ O) (iv) [where n is 1.8 to 3.0 and w is a number of 1 to 6 Represent. ]
Is preferably represented by As the crystalline aluminosilicate (zeolite), synthetic zeolites having an average primary particle size of 0.1 to 10 μm represented by A-type, X-type and P-type zeolites are preferably used. The zeolite may be blended as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry.

In the present invention, the aluminosilicate is incorporated in the composition in an amount of 5 to 30% by weight, preferably 5 to 25% by weight. When the amount of the aluminosilicate is out of this range, the detergency decreases.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION In addition to the components (a) to (c), the following builders can be added to the high-density granular detergent composition of the present invention.

<Amorphous Aluminosilicate> In the present invention, an amorphous aluminosilicate can be used in addition to the crystalline aluminosilicate. As the amorphous aluminosilicate, one containing silicon as SiO ₂ in an amount of 30% by weight or more, preferably 40% by weight or more is preferable. In addition, when a 5% dispersion having a pH of 9 or more is used, Deterioration of detergent solubility after high humidity storage is further improved.

Examples of the amorphous aluminosilicate used in the present invention include those represented by the following general formula (i):
These have high oil absorption and high cation exchange capacity. a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (i) (where M is an alkali metal atom, and a, b, and c represent the number of moles of each component. , Generally 0.7 ≤ a ≤ 2.0, 0.8 ≤ b <
4, c is any positive number. In particular, the following general formula (ii): Na ₂ O.Al ₂ O ₃ .b (SiO ₂ ) .c (H ₂ O) (ii) wherein b is 1.8 to 3.2 and c is a number of 1 to 6. Represents ]
Is preferably represented by In particular, since amorphous aluminosilicate has not only ion exchange capacity but also oil absorption capacity,
When a liquid surfactant is used, it is an important component for maintaining powder properties.

A method for producing such an amorphous aluminosilicate will be briefly described. First, the molar ratio between SiO ₂ and M ₂ O (M means an alkali metal) is SiO ₂ / M ₂ O = 1.0 to 4.0, and the molar ratio between H ₂ O and M ₂ O is H ₂ O / M _{In an} aqueous solution of an alkali metal silicate in which ₂ O = 12 to 200, the molar ratio of M ₂ O and Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0, and H ₂ O and M ₂ O A low alkali aqueous solution of an alkali metal aluminate having a molar ratio of H ₂ O / M ₂ O = 6.0 to 500 is applied at 15 to 60 ° C., preferably 30 to 50
Add under vigorous stirring at a temperature of ° C. Further, an aqueous solution of an alkali metal silicate may be added to the aqueous solution of an alkali metal aluminate. The resulting white precipitate slurry is then
10-100 minutes at a temperature of 70-100 ° C, preferably 90-100 ° C
It can be advantageously obtained by performing a heat treatment for not more than time, preferably not more than 5 hours, followed by filtration, washing and drying. By this method, an amorphous aluminosilicate having an ion exchange capacity of 100 CaCO ₃ mg / g or more and an oil absorption capacity of 200 ml / 100 g or more can be easily obtained.

When the amorphous aluminosilicate is mixed, the amount of the water-insoluble substance is substantially increased, which is disadvantageous in terms of solubility. In such a case, it is desirable to use an amorphous aluminosilicate having the following specific properties. That is, by selecting an amorphous aluminosilicate having a pH of the 5% dispersion of 9.0 or more, a high-density detergent composition whose solubility is not deteriorated particularly when stored under high humidity conditions is obtained. be able to. Here, the pH of the 5% dispersion of the amorphous aluminosilicate is JIS K 62
Measured based on 20. Specifically, about 5 g of the sample is weighed and placed in a hard Erlenmeyer flask, 100 ml of water containing no carbonic acid is added, the stopper is closed, and the mixture is shaken for 5 minutes. The pH is measured by the glass electrode method (JIS Z 8802, 7.2.3) using the liquid after shaking as a test liquid. When the alkalinity of the detergent is very high or the storage conditions are very severe, an amorphous aluminosilicate that satisfies the condition that the amount of dissolution in a 2% aqueous NaOH solution is 0.5 g or less is selected. Good. That is, 10 g of an amorphous aluminosilicate is dispersed in 100 ml of a 2% aqueous NaOH solution, and the mixture is stirred at a constant temperature of 25 ° C. for 16 hours, and SiO ₂ in the filtrate is colorimetrically determined.
6, 1976), the amount of which is less than 0.5 g as an amorphous aluminosilicate.

<Crystalline silicate> In the present invention, it is particularly preferable to add a crystalline silicate. The crystalline silicate is preferably an alkali metal salt of silicic acid (SiO ₂ ), in particular, an alkali metal silicate having SiO ₂ / M ₂ O (where M represents an alkali metal) of 0.5 to 2.6. Is preferably used.
Crystalline silicate known conventionally SiO ₂ / Na ₂ O is 1.9 to 4.
Although it is 0, if the ratio exceeds 2.6, it may not be suitable for the formulation of the high-density detergent targeted by the present invention.

The preferred crystalline silicate used in the present invention has the following composition. _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (II) wherein, M represents a Group Ia elements of the periodic table, Me represents the periodic One or more combinations selected from the group IIa element, IIb element, IIIa element, IVa element or VIII element shown in the table, y / x = 0.5 to 2.6, z / x = 0.01 to 1.0 ,
w = 0 to 20, and n / m = 0.5 to 2.0. ] _{M 2 O · x '(SiO} 2) · y' (H 2 O) (III) wherein, M represents an alkali metal, x '= 1.5~2.6, y'
= 0 to 20. ].

First, the crystalline silicate represented by the general formula (II) will be described.

In the general formula (II), M is selected from Group Ia elements of the periodic table, and examples of Group Ia elements include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to constitute the M ₂ O component.

Me is a group IIa element, a group IIb element of the periodic table,
It is selected from Group IIIa element, Group IVa element or Group VIII element, and includes, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. These may be used alone or as a mixture of two or more. For example, MgO, Ca
O and the like may constitute the Me _m O _n component are mixed.

In the general formula (II), y / x is
It is 0.5 to 2.6, preferably 1.5 to 2.2. y / x
If it is less than 0.5, the water resistance is insufficient and the caking properties, the solubility, and the powder properties of the detergent composition are significantly adversely affected. On the other hand, when y / x exceeds 2.6, the alkalinity becomes low and the alkalinity becomes insufficient, and the ion exchange ability also becomes low and the ion exchange is insufficient.
In the general formula (II), z / x is 0.01 to 1.0, preferably 0.02 to 0.9. If z / x is less than 0.01, the water resistance is insufficient, and if z / x exceeds 1.0, the ion exchange capacity is lowered and the ion exchange capacity is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the y / x ratio and the z / x ratio described above. In addition,
As described above, when x (M ₂ O) is, for example, x ′ (Na ₂ O) · x ″ (K ₂ O) ·, x is x ′ + x ″. Such a relationship is
(Me _m O _n) z when the component consists of more than two
The same applies to. Also, n / m indicates the number of oxygen ions coordinated to the element, and is substantially 0.5, 1.0,
It is selected from the values of 1.5 and 2.0.

The crystalline silicate represented by the general formula (II) is M ₂
It is _composed of three components, O ₂ , SiO ₂ and Me _{m On} . Accordingly, in order to produce the crystalline silicate represented by the general formula (II), each component is required as a raw material. In the present invention, a known compound is appropriately used without any particular limitation.
For example, M ₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, as a raw material of the M ₂ O component, NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO ₄
Etc. is, as a material of Me _m O _n component, CaCO _3, MgCO _3, Ca
(OH) ₂ , Mg (OH) ₂ , MgO ₂ , ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

The method for preparing the crystalline silicate represented by the general formula (II) is to mix the above-mentioned raw material components at a predetermined quantitative ratio so as to obtain the desired x, y, z values of the crystalline silicate. And usually 300 ~
1500 ° C, preferably 500-1000 ° C, more preferably 600
A method of crystallization by firing at a temperature in the range of -900 ° C is exemplified. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is inferior, and if it exceeds 1500 ° C., the particles become coarse and the ion exchange ability is reduced. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace.

The thus-obtained crystalline silicate represented by the general formula (II) is obtained by adding 11% by weight to a 0.1% by weight aqueous dispersion.
It shows the above pH and shows excellent alkalinity. In addition, the alkali buffering effect is particularly excellent, and the alkali buffering effect is superior to that of sodium carbonate or potassium carbonate.

The crystalline silicate represented by the general formula (II) is
It has an ion exchange capacity of at least 100 CaCO ₃ mg / g or more, preferably 200 to 600 CaCO ₃ mg / g, and is one of the substances having an ion trapping ability in the present invention.

The crystalline silicate represented by the general formula (II) is
As described above, it has an alkaline ability and an alkaline buffering effect, and further has an ion exchange ability. Therefore, by appropriately adjusting the compounding amount, the above-mentioned washing conditions can be suitably adjusted.

The crystalline silicate represented by the general formula (II) preferably has an average particle size of 0.1 to 100 μm, more preferably 1 to 60 μm. If the average particle size exceeds 100 μm, the rate of onset of ion exchange tends to be slow, leading to a decrease in detergency. In addition, when it is less than 0.1 μm, the hygroscopicity and CO ₂ absorption increase due to an increase in specific surface area,
Quality degradation tends to be significant. Here, the average particle size is the median size of the particle size distribution.

The crystalline silicate having such an average particle size and particle size distribution can be prepared by pulverization using a pulverizer such as a vibration mill, a hammer mill, a ball mill, a roller mill and the like.

Next, the crystalline silicate represented by the general formula (III) will be described. The crystalline silicate of the general formula _{(III) M 2 O · x} '(SiO 2) · y' (H 2 O) (III) wherein, M represents an alkali metal, x '= 1.5 to 2.6 , Y '
= 0 to 20. Is represented by the general formula (I
II) It is preferable that x ′ and y ′ in 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and those having a cation exchange capacity of 100 to 400 CaCO ₃ mg / g can be used. It is one of the substances having the function. The crystalline silicate represented by the general formula (III) thus has an alkaline ability and an alkaline buffering effect,
Further, since it has an ion exchange ability, the above-mentioned washing conditions can be suitably adjusted by appropriately adjusting the amount thereof.

The crystalline silicate represented by the general formula (III) is
JP-A-60-227895 describes its production method,
Generally, amorphous glassy sodium silicate is 200 ~ 1000 ℃
And crystallized by firing. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (196
6), Z. Kristallogr., 129, 396-404 (1969). The crystalline silicate represented by the general formula (III) is, for example, “Na-SKS-6” (δ-
Powders and granules can be obtained as Na ₂ Si ₂ O ₅ ). In the present invention, the crystalline silicate represented by the general formula (III) preferably has an average particle diameter of 0.1 to 100 μm, like the crystalline silicate represented by the general formula (II),
More preferably, it is 1 to 60 μm.

In the present invention, the crystalline silicate represented by the general formula (II) and the crystalline silicate represented by the general formula (III) can be used alone or in combination of two or more. In addition, of the alkali agents to be incorporated in the composition, preferably 30 to 100% by weight, more preferably 50 to 100% by weight.
It is desirable to account for 0% by weight.

In the present invention, the crystalline silicate is preferably contained in the composition in an amount of 1 to 40% by weight, particularly 3 to 20% by weight.

The <polycarboxylate> builder has an effect of dispersing solid particle stains from clothes into a washing bath and an effect of preventing the particles from reattaching (recontaminating) to clothes.
For this purpose, the following (IVa) having a molecular weight of several hundred to 100,000
It is preferable to blend a polycarboxylate such as a copolymer represented by the formula or / and a homopolymer represented by the formula (Va).

[0051]

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Wherein Z is an olefin having 1 to 8 carbon atoms;
Maleic acid (anhydride) such as acrylic acid, methacrylic acid, itaconic acid, methallyl sulfonic acid, or a salt of a copolymer of maleic anhydride and a monomer copolymerizable with maleate, where m is a molecular weight of several hundred It is a value indicating ~ 100,000. M is _{Na, K, NH 4, H} . )

[0053]

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(In the formula, p is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. L is a value such that the molecular weight of the homopolymer is several hundred to 100,000. there. homopolymers Na, K, NH ₄ are salified.) (IVa) the amount of copolymer or / and (Va) expression homopolymer of expression relative to the detergent composition 100 parts by weight, 1 to 8 parts by weight, preferably 2 to 6 parts by weight. Acrylic acid among these polycarboxylate - maleic acid copolymer salt and polyacrylic acid salt (Na, K, NH ₄₎ are particularly excellent. The molecular weight is suitably from 1,000 to 80,000.

<Other builders> In addition to the above builders, the following inorganic or organic builders can be used. (I) Inorganic builder 1) Alkaline salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate 2) Phosphates (sodium, potassium, etc.) such as orthophosphate, pyrophosphate, tripolyphosphate 3) Neutral salt such as sodium sulfate (II) Organic builder 1) Salt of phosphonic acid such as ethane-1,1-diphosphonic acid, ethane-1,2-triphosphone 2) Polyethylene glycol, polyvinyl alcohol ,
Polyvinylpyrrolidone, carboxymethyl cellulose,
Polymer electrolytes such as polyaspartic acid 3) Organic acid salts such as diglycolic acid and oxydisuccinic acid.

Further, the following components can be blended as components other than the builder.

Examples of the bleaching agent include sodium percarbonate, sodium perborate (preferably a monohydrate), and an adduct of sodium hydrogen peroxide and the like. Particularly, sodium percarbonate is preferable.

Examples of the bleach activator include tetraacetylethylenediamine, acetoxybenzenesulfonate, and organic peracids described in JP-A-59-22999, JP-A-63-258447, and JP-A-6-316700. Examples include a precursor or a metal catalyst in which a transition metal is stabilized with a sequestering agent.

Enzymes (enzymes which essentially perform an enzymatic action during the washing step) can be classified according to their reactivity. Hydrolases, hydrolases, oxidoreductases, tesmolases, transferases and isomerases However, any of them can be applied to the present invention. Particularly preferred are hydrolases, including proteases, esterases, lipases, pectinases, carbohydrases, nucleases, cellulases and amylases.

Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promerin, carboxypeptidases A and B, aminopeptidases, aspergillopeptidases A and B. As commercial products, Savinase, Alcalase (Novo Industries), API 21 (Showa Denko KK), Maxacal (Gist Procaides), Protease K-14 or K-16 described in JP-A-5-43892. There is.

Specific examples of esterases include gastric lipase, bankreatic lipase, plant lipases,
There are phospholipases, cholinesterases and phosphotases.

As a specific example of the lipase, a commercially available lipase such as Lipolase (Novo Industries) can be used.

Specific examples of carbohydrase include cellulase, maltase, saccharase, amylase, lysozyme, α-glycosidase and β-glycosidase.

As cellulase, commercially available cellzyme (Novo Industry) and cellulase described in claim 4 of JP-A-63-264699 can be used. As amylase, commercially available termamyl (Novo Industry) and the like can be used. Can be used.

As an enzyme stabilizer, a reducing agent (sodium sulfite, sodium hydrogen sulfite, calcium salt, magnesium salt, polyol, boron compound, etc.) can be used.

Various bluing agents can be added as required. For example, those having the structures of the following formulas (i) and (ii) are recommended.

[0067]

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(Wherein D ₁ represents a blue-violet monoazo, disazo or anthraquinone dye residue, and X ₁ and
Y ₁ is a hydroxyl group; an amino group, a hydroxyl group, a sulfonic acid group, an aliphatic amino group which may be substituted with a carboxylic acid group or an alkoxy group; a halogen atom, a hydroxyl group, a sulfonic acid group;
It represents an aromatic amino group or a cycloaliphatic amino group which may be substituted with a carboxylic acid group, a lower alkyl group or a lower alkoxy group, and R represents a hydrogen atom or a lower alkyl group. However, when R ₁ represents a hydrogen atom, and X ₁ and Y ₁ simultaneously represent a hydroxyl group or an alkanolamino group, and _one of X ₁ and Y ₁ is a hydroxyl group, and the other is an alkanolamino group. Except in some cases. n represents an integer of 2 or more. )

[0069]

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(Wherein, D ₂ represents a blue to purple azo or anthraquinone dye residue, R represents a hydrogen atom or a lower alkyl group, and X ₂ and Y ₂ represent the same or different alkanolamino groups or hydroxyl groups. The anti-caking agent includes paratoluenesulfonate, xylenesulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, magnesium oxide and the like. In addition, a porous material such as finely divided silica can be used as a carrier for a nonionic surfactant. Clay (smectite-like clay) is also effective as a softening agent.

Examples of the antioxidant include tert-butylhydroxytoluene, 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), and 2,2′-butylidenebis-
(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1′-bis- (4-hydroxyphenyl) cyclohexane and the like.

As fluorescent dyes, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) A) a naphthothiazole derivative, a 4,4'-bis (triazol-2-yl) stilbene derivative, a bis (triazinylamino) stilbene disulfonic acid derivative, or 1 to 2% by weight in the composition; Can be contained.

As the fragrance, a fragrance conventionally used in detergents, for example, a fragrance described in JP-A-63-101496 can be used.

Although the high-density detergent composition of the present invention is a powdery or lumpy composition, its production method is not particularly limited, and a conventionally known method can be used. Preferably, it is a granular composition having a high bulk density. The method for increasing the bulk density is, for example, a method of spraying a nonionic surfactant onto spray-dried particles to increase the density, or a method of increasing the density while directly absorbing nonions into a powder component containing an oil-absorbing carrier. Examples thereof include JP-A-61-69897 and JP-A-61-69897.
69899, JP-A-61-69900, JP-A-2-22
2498, JP-A-2-222499, JP-A-3-3319
No. 9, JP-A-5-86400, JP-A-5-209200
Can be referred to. Also,
A small amount of the crystalline aluminosilicate may be added during granulation or immediately before the end of granulation in order to use it as a surface modifier for the granulated material. 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 aminopolycarboxylic acid compound of the component (a) of the present invention dissociates stepwise depending on pH, and dissociates completely at pH 11 or higher. On the other hand, at a high pH, the hydrooxo complex of the metal ion becomes stable and affects the chelate formation.
Due to such effects, the chelate stability constant shows pH dependence. In the case of calcium and magnesium which are hardness components in water, chelation formation by an aminopolycarboxylic acid compound is more effective when used at a high pH (pH 11 to 12). Therefore, in order to effectively exhibit the chelating ability of the aminopolycarboxylic acid compound of the present invention, it is desirable that the composition be capable of maintaining a high pH of the washing solution. Among the above-mentioned inorganic builders, sodium carbonate and sodium silicate are typical alkali agents, and sodium silicate is particularly high.
It is more preferable because it gives pH. However, when these are blended in large amounts, a relatively large amount of water-insoluble components may be formed with zeolite during storage of the detergent. Therefore, attention must be paid to the amounts of sodium carbonate and sodium silicate. To solve this problem, the above-mentioned crystalline silicate is effective as a multifunctional builder having both functions of zeolite and sodium silicate, and a layered crystalline silicate is particularly preferable. By using a crystalline layered silicate, a high pH equivalent to that of sodium silicate can be obtained, and the amount of water-insoluble matter generated during storage is extremely small. In the present invention, the crystalline layered silicate is preferably blended in an amount of 1 to 40% by weight, more preferably 3 to 20% by weight.

The average particle size of the high-density granular detergent composition of the present invention is desirably 200 to 1000 μm, particularly preferably 200 to 600 μm, in order to obtain preferable powder properties. The bulk density of the detergent composition of the present invention is about 0.5 to 1.2 g / cm ³ , preferably about 0.6 to 1.0 g / cm ³ .

The detergent composition of the present invention is used at a concentration suitable for each washing depending on the washing method such as washing machine washing and pickling washing, as well as the amount of clothes and water, the degree of dirt, and the method of using a machine. can do. For example, in the case of washing in a washing machine, a washing concentration of 0.03 to 0.3% by weight can be used.

[0078]

According to the present invention, a high-density granular detergent composition having further improved detergency in a system using an organic builder and an inorganic builder excellent in biodegradability is obtained.

[0079]

BEST MODE FOR CARRYING OUT THE INVENTION

[0080]

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

Synthesis Example 1 <Synthesis of Compound APC-1> Compound APC-1 [Chelate compound represented by formula (IV)]
Was synthesized by the following method. In a 1-liter four-necked flask, 155 g of DL-serine, 40% aqueous sodium hydroxide solution
155 g and 440 g of water were charged and the temperature was raised to 60 ° C. 50% here
A monochloroacetic acid aqueous solution (280 g) was added dropwise at 70 ° C. over 6 hours. During that time, the pH in the reaction system was maintained at 11 using a 40% aqueous sodium hydroxide solution. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours. As a result, N-carboxymethyl-serine 2
1320 g of an aqueous solution containing 17.4% of Na salt was obtained. To this, 122 g of a 40% aqueous sodium hydroxide solution, 31.3 g of hydrocyanic acid and 51 g of acetaldehyde were added dropwise at 105 ° C. over 6 hours. As a result of aging at the same temperature for 4 hours, 1510 g of an aqueous solution containing 21% of N- (1-carboxyethyl) -N- (carboxymethyl) serine 3Na salt [APC-1] having the following structure was obtained.

[0082]

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[0083] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 2 <Synthesis of Compound APC-2> Compound APC-2 [Chelate compound represented by general formula (V)]
Was synthesized by the following method. In a 1 liter four-necked flask, 105 g of DL-serine, 40% aqueous sodium hydroxide solution
100 g and 880 g of water were charged, and 220 g of a 40% aqueous sodium hydroxide solution, 58.1 g of hydrocyanic acid and 95 g of acetaldehyde were added to 105 g of water.
The solution was added dropwise at 6 ° C over 6 hours. After aging at the same temperature for 4 hours, N, N-bis (1-carboxyethyl) having the following structure was obtained.
1320 g of an aqueous solution containing 22% of serine 3Na salt [APC-2] was obtained.

[0084]

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[0085] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 3 <Synthesis of Compound APC-3> Compound APC-3 [Chelate compound represented by general formula (VI)]
Was synthesized by the following method. A 2-liter four-neck flask was charged with 79 g of DL-alanine, 113 g of maleic acid, 274 g of a 40% aqueous sodium hydroxide solution, and 440 g of water.
The temperature rose. Aged at the same temperature for 4 hours. As a result, N-
906 g was obtained containing 25.1% of (1-carboxyethyl) aspartic acid trisodium salt. Here, 318 g of a 50% aqueous monochloroacetic acid solution was added dropwise at 70 ° C. over 6 hours. During that time, use a 40% aqueous sodium hydroxide solution and adjust the pH in the reaction system.
Was kept at 11. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours. As a result, N- (1-carboxyethyl) -N-
(Carboxymethyl) aspartic acid 4Na salt [APC-3]
1560 g of an aqueous solution containing 17% was obtained.

[0086]

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[0087] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 4 <Synthesis of Compound APC-4> Compound APC-4 [chelate compound represented by formula (VII)] was synthesized by the following method. 133 g of L-aspartic acid, 200 g of a 40% aqueous sodium hydroxide solution and 880 g of water were charged into a 2 liter four-neck flask, and 220 g of a 40% aqueous sodium hydroxide solution, 58.1 g of hydrocyanic acid and 95% of acetaldehyde were added.
g was added dropwise at 105 ° C. over 6 hours. As a result of aging at the same temperature for 4 hours, 1545 g of an aqueous solution containing 20% of 4Na salt of N, N-bis (1-carboxyethyl) -aspartic acid [APC-4] having the following structure was obtained.

[0088]

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[0089] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 5 <Synthesis of Compound APC-5> Compound APC-5 [a chelate compound represented by the general formula (VIII)] was synthesized by the following method. In a 2 liter four-necked flask, 74 g of DL-alanine, 140 g of monosodium epoxysuccinate, 171 g of a 40% aqueous sodium hydroxide solution, water
480 g was charged and heated to 70 ° C. Aged at the same temperature for 3 hours. As a result, N- (1-carboxyethyl) N-
860 g of an aqueous solution containing 27% of (1,2-dicarboxy-2-hydroxyethyl) amine trisodium salt was obtained. Here, 307 g of a 50% aqueous monochloroacetic acid solution was added dropwise at 70 ° C. over 6 hours. Meanwhile, the pH in the reaction system was maintained at 11 using a 40% aqueous sodium hydroxide solution. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours, and N- (1-carboxyethyl) -N- (carboxymethyl) -N- (1,2-dicarboxy-2-hydroxyethyl) amine tetrasodium salt having the following structure was used. 1490 g of an aqueous solution containing 18% of [APC-5] was obtained.

[0090]

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A part of the obtained aqueous solution was freeze-dried, and ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 6 <Synthesis of Compound APC-6> Compound APC-6 [Chelate compound represented by general formula (IX)]
Was synthesized by the following method. In a 1-liter four-necked flask, 149 g of 2-amino-3-hydroxysuccinic acid, 40%
Charge 200g of sodium hydroxide aqueous solution and 880g of water, and add 40g
220 g of a 5% aqueous sodium hydroxide solution, 58.1 g of hydrocyanic acid and 95 g of acetaldehyde were added dropwise at 105 ° C. over 6 hours. As a result of aging at the same temperature for 4 hours, N, N-bis (1-carboxyethyl) -N- (1,2-dicarboxy-2-hydroxyethyl) amine 4Na salt [APC-6] having the following structure was obtained.
1560 g of an aqueous solution containing 1% was obtained.

[0092]

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[0093] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 7 <Synthesis of Compound APC-7> Compound APC-7 [Chelate compound represented by general formula (X)]
Was synthesized by the following method. In a 2 liter four-necked flask, 141 g of glutamic acid, 40% aqueous sodium hydroxide solution
202 g and 630 g of water were charged and the temperature was raised to 60 ° C. 50% here
181 g of monochloroacetic acid aqueous solution was added dropwise at 70 ° C. over 6 hours. During that time, the pH in the reaction system was maintained at 11 using a 40% aqueous sodium hydroxide solution. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours. As a result, N- (1-carboxymethyl)
1340 g of an aqueous solution containing 16% of glutamic acid 3Na salt was obtained.
To this, 85 g of a 40% aqueous sodium hydroxide solution, 21.8 g of hydrocyanic acid and 36 g of acetaldehyde were added dropwise at 105 ° C. for 6 hours. Aged at the same temperature for 4 hours to obtain N- (1-carboxyethyl) -N- (carboxymethyl) glutamic acid 4Na having the following structure:
1480 g of an aqueous solution containing 18% of the salt [APC-7] was obtained.

[0094]

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[0095] A portion of the resulting aqueous solution was lyophilized, ¹ H
-The result of having measured the NMR spectrum is shown below. Synthesis Example 8 <Synthesis of Compound APC-8> Compound APC-8 [Chelate compound represented by general formula (XI)]
Was synthesized by the following method. In a 1-liter four-necked flask, 147 g of L-glutamic acid, 200 g of a 40% aqueous sodium hydroxide solution and 880 g of water were charged, and 220 g of a 40% aqueous sodium hydroxide solution, 58.1 g of hydrocyanic acid and 95 g of acetaldehyde were added.
It was added dropwise at 105 ° C. over 6 hours. After aging at the same temperature for 4 hours, an aqueous solution 1 containing 22% of N, N-bis (1-carboxyethyl) -glutamic acid 4Na salt [APC-8] having the following structure was obtained.
560 g were obtained.

[0096]

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A part of the obtained aqueous solution was freeze-dried, and ¹ H
-The result of having measured the NMR spectrum is shown below. Example 1 <Preparation of high-density granular detergent composition> The product 1 of the present invention in Table 1 was prepared by the following method. Aminopolycarboxylic acid compound (APC-
1) 1 kg, crystalline aluminosilicate 0.5 kg, LAS 2k
g, 0.3 kg of AA-MA copolymer, 0.2 kg of FA and 1 kg of sodium carbonate, 0.5 kg of sodium silicate, sodium sulfate used for balance, 0.05 kg of fluorescent dye (4,4'-bis- (2-sulfostyryl) -biphenyl salt) And a water slurry of 60% solids was prepared from 0.1 kg of PEG and PEG, and particles obtained by spray-drying the slurry were put into a Loedige mixer (manufactured by Matsusaka Giken Co., Ltd.), and 1.0 kg of crystalline aluminosilicate was further added. In addition, 0.5 kg of AE heated to 70 ° C is gradually dropped into a place where these are mixed,
Granulation was performed. Further, 30 seconds before the completion of granulation, 0.5 kg of crystalline aluminosilicate was added to obtain a high-density granular detergent composition (average particle diameter: 530 μm, bulk density: 816 g / liter). With respect to other products of the present invention and comparative products, high-density granular detergents were prepared according to the above-mentioned schemes, with each mixing ratio. The obtained high-density granular composition was subjected to a detergency test and a solubility test by the following methods. Table 1 shows the results.
It is shown in FIG.

<Detergency test> (Preparation of artificially stained cloth) An artificially stained cloth having the following composition was adhered to the cloth to prepare an artificially stained cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The process of adhering the artificially contaminated liquid to the cloth to produce the artificially contaminated cloth is based on the cell capacity of the gravure roll.
The drying was performed at 8 cm ³ / cm ² , a coating 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 gold cloth 2003 (manufactured by Tanito Shoten). [Composition of artificial contaminant] Lauric acid 0.44% by weight Myristinic acid 3.09% by weight Pentadecanoic acid 2.31% by weight Palmitic acid 6.18% by weight Heptadecanoic acid 0.44% by weight Stearic acid 1.57% by weight Oleic acid 7.75% by weight Trioleic acid 13.06% by weight Palmitic acid n-hexadecyl 2.18% by weight squalene 6.53% by weight Egg white lecithin liquid crystal 1.94% by weight Kanuma red clay 8.11% by weight Carbon black 0.01% by weight Tap water balance.

(Cleaning Conditions and Evaluation Method) Five liters of the artificially contaminated cloth of 10 cm × 10 cm prepared above were placed in 1 liter of an aqueous cleaning agent solution for evaluation, and washed at 100 rpm with a tergotometer. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Washing agent concentration 0.067% Water hardness 4 ° DH Water temperature 20 ° C Rinse for 5 minutes with tap water Washing power is the self-recording color at 550 nm of the original cloth before and after cleaning. The cleaning rate (%) was determined by the following equation, and the average of the measured values of the five sheets was shown as the cleaning power.

[0100]

(Equation 1)

<Solubility test> Aperture 710 μm and 1000 μm
The size of the detergent particles is adjusted using a sieve. Take 1 liter of 5 ° C tap water into a 1 liter beaker and stir with a stirrer (about 550 rpm). Detergent particles are charged, and the change over time in electrical conductivity is measured. The electrical conductivity meter used was "CM-60S" manufactured by Toa Electric Industry Co., Ltd. Based on the electrical conductivity when the detergent particles are completely dissolved, the time to reach 90% of the electrical conductivity was solubility index detergent as T _90.

[0102]

[Table 1]

[0103]

[Table 2]

APC-1: a compound represented by the formula (IV) (M = sodium) APC-2: a compound represented by the formula (V) (M = sodium) APC-3: a formula (VI) APC-4: A compound represented by the formula (VII) (M = sodium) APC-5: A compound represented by the formula (VIII) (M = sodium) APC -6: Compound represented by formula (IX) (M = sodium) APC-7: Compound represented by formula (X) (M = sodium) APC-8: Compound represented by formula (XI) (M = sodium) ・ LAS: straight chain alkyl (C ₁₂ ) sodium salt of benzenesulfonic acid ・ AS: sodium salt of dodecyl alcohol sulfate ・ SFE: methyl ester of α-sulfo fatty acid (coconut fatty acid composition) ・ FA: sodium salt of palmitic acid・ AE: Polyoxyethylene dodecyl ether (HLB = 1
0.2) ・ AG: dodecyl glycoside (average degree of sugar condensation = 1.5) ・ MEGA: dodecanoyl-N-methylglucamide ・ Crystalline aluminosilicate: composition M ₂ O ・ Al ₂ O ₃・ 2SiO ₂・ 2H
₂ O, average particle diameter 4 μm, ion exchange capacity 290 CaCO ₃ mg / g ・ silicate (II): composition M ₂ O ・ 1.8 SiO ₂・ 0.02 M′O (here,
M: Na, K, K / Na = 0.03, M '= Ca, Mg, Mg / Ca = 0.01)
, Ion exchange capacity 290CaCO ₃ mg / g, average particle size 30μm
(Crystalline silicate represented by the general formula (II)) • Silicate (III): Composition M ₂ O · 2SiO ₂ , ion exchange capacity 22
4CaCO ₃ mg / g, average particle size 30 μm, (crystalline silicate represented by general formula (III)) AA-MA copolymer: Na salt of acrylic acid / maleic acid (molar ratio 7/3) copolymer, average PEG: polyethylene glycol having an average molecular weight of 7000 • Common components: enzyme [Sabinase 12.0TW (manufactured by Novo Nordisk), lipolase 100T (manufactured by Novo Nordisk),
Cellzyme 0.1T (Novo Nordisk), Termamill
1%, fluorescent dye 0.5% and sodium sulfate, and the total amount was adjusted to 100% with sodium sulfate.

Claims (11)

[Claims] (A) 0.1 to 30% by weight of an aminopolycarboxylic acid compound represented by the following general formula (I): (Wherein, R ¹ and R ² are the same or different, and each is H or -C
H ₃ , at least ^one of R ¹ and R ² is —CH ₃ , and R ³ is
—CH ₂ COOM, —CH (OH) COOM, —CH ₂ CH ₂ COOM or —CH ₂ OH, and M is H 2, Na, K or NH ₄ . A high-density granular detergent composition containing (b) 10 to 50% by weight of a surfactant, (c) 5 to 30% by weight of a crystalline aluminosilicate and having a bulk density of 0.6 to 1.2 g / ml. 2. The high-density granular detergent composition according to claim 1, which contains 1 to 40% by weight of a crystalline silicate of the following formula (II) and / or (III). _{x (M 2 O) · y} (SiO 2) · z (Me m O n) · w (H 2 O) (II) ( wherein, M represents a Group Ia elements of the periodic table, Me represents a Group IIa An element, a group IIb element, a group IIIa element, a group IVa element, or a combination of two or more elements selected from group VIII elements,
y / x = 0.5-2.6, z / x = 0.01-1.0, w = 0-2
0, n / m = 0.5 to 2.0. ) M ₂ O · x ′ (SiO ₂ ) · y′H ₂ O (III) (wherein M represents an alkali metal, x = 1.5 to 2.6, y ′)
= 0 to 20. ) 3. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (IV). Embedded image 4. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (V). Embedded image 5. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (VI). Embedded image 6. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (VII). Embedded image 7. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (VIII). Embedded image 8. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (IX). Embedded image 9. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (X). Embedded image 10. The high-density granular detergent composition according to claim 1, wherein the aminopolycarboxylic acid compound represented by the general formula (I) is a compound represented by the following formula (XI). Embedded image 11. The surfactant of component (b) has 10 to 10 carbon atoms.
Sulfate of 18 linear or branched primary or secondary alcohols, sulfate of ethoxylated alcohol having 8 to 20 carbon atoms, alkylbenzene sulfonate, paraffin sulfonate, α-olefinsulfonic acid Salts, α-sulfofatty acid salts, α-sulfofatty acid alkyl ester salts, polyoxyalkylene alkyl ethers,
The polyoxyalkylene alkylphenyl ether, a polyoxyalkylene sorbitan fatty acid ester, a polyoxyalkylene glycol fatty acid ester, or one or more selected from a polyoxyethylene polyoxypropylene block polymer.
Item 7. A high-density granular detergent composition according to Item 1.