JPH09279199A - High-density granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject detergent composition with bulk density within a specific range, excellent in biodegradability and safety and further improved in detergency, comprising a anionic surfactant and a specific carboxybetaine-type surfactant in specified proportions. SOLUTION: This detergent composition with a bulk density of 0.5-1.2g/mL is obtained by blending (A) 10-50wt.% of an anionic surfactant (e.g. higher fatty acid salt) with (B) 1.0-20wt.% of a carboxybetaine-type surfactant of formula I (R1 is a 10-20C alkyl or alkenyl; R2 and R3 are each 1-3C alkyl, alkeneyl or H) in the the weight ratio B/A of (1:100) to (100:100) followed by 1-60-wt.% of an aliminosilicate and 1-40wt.% of a crystalline silicate of formula II (M is a group I a element; Me is at least one kind selected from groups IIa, IIb, IIIa, IVa and VIII elements; y/x=0.5-2.6; z/x=0.01-1.0; (w) =0-20; n/m=0.5-2.0) and then drying, grinding and granulation.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a high-density granular detergent composition. More specifically, the present invention relates to a high-density granular detergent composition in which the detergency is further improved by adding an appropriate amount of a carboxybetaine type surfactant having excellent biodegradability and safety to an anionic surfactant.

[0002]

2. Description of the Related Art A detergent for clothes is used for solubilizing stains, a surfactant for dissolving and dispersing fibers in a washing liquid, an alkaline agent for promoting decomposition and solubilization (emulsification) of stains, and dispersing stains. It is basically composed of a polymer compound, a sequestering agent for removing calcium and magnesium, etc., which reduce the ability of the surfactant from the washing liquid. Of these components, a substance that does not exhibit cleaning performance by itself, but has the purpose of improving the cleaning power when combined with a surfactant, is generally called a detergent builder or simply a builder. Builders are extremely important substances for more effectively expressing the performance of surfactants.

Surfactants play a major role in removing dirt from fibers as described above. Surfactants used in detergents are roughly classified into those mainly composed of anionic substances and those mainly composed of nonionic substances. As the surfactant mainly used for anionic properties, an alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms, and 10 to 18 carbon atoms
Of higher alcohols such as sulfate ester salts, α-olefin sulfonates, α-sulfo higher fatty acid ester salts, and alkane sulfonates (SAS), which are mainly used for nonionic surfactants. Examples of the agent include polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether. Examples of these are, for example, Japanese Patent Publication No. 64-10039 and Japanese Patent Publication No. 4-43119.
JP-A-5-66440, JP-A-4-339898, JP-A-5-5100, JP-A-6-9999, and JP-A-6-100000.

The high density, compactness and miniaturization of detergents are progressing in accordance with market demands such as resource saving, labor saving and transportation cost reduction. However, the above-mentioned surfactants are still used, and there is a demand for a surfactant having a higher cleaning performance suitable for high-density detergents.

[0005]

In recent years, in addition to the above requirements, there is a concern about the problem of the influence of detergents on the environment, and biodegradability of high-density detergents is being studied. Carboxybetaine-type surfactants are excellent in biodegradability and excellent in safety, but the optimum combination formulation for a combination system with an anionic surfactant when preparing a high-density detergent has not yet been known. Under such circumstances, an object of the present invention is to provide a high-density granular detergent having improved detergency in a system containing an anionic surfactant and a carboxybetaine type surfactant.

[0006]

Means for Solving the Problems As a result of various investigations by the present inventors, an anionic surfactant is mainly used as a surfactant, and a carboxybetaine type surfactant having a specific structure is used at a specific blending ratio. It was found that the cleaning property was remarkably enhanced, and the present invention was completed.

That is, the present invention comprises: (a) 15 to 50% by weight of anionic surfactant (b) 1.0 to 20% by weight of carboxybetaine type surfactant represented by the following general formula

[0008]

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(Wherein R ₁ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₂ and R ₃ are alkyl groups or alkenyl groups having 1 to ₃ carbon atoms), and
(b) / (a) A high-density granular detergent composition having a weight ratio of 1/100 to 100/100 and a bulk density of 0.5 to 1.2 g / ml is provided. Hereinafter, the high-density granular detergent composition of the present invention will be described.

<(A) Anionic Surfactant> The anionic surfactant used in the present invention includes a higher fatty acid salt having 8 to 18 carbon atoms, a linear or branched primary or secondary chain having 8 to 18 carbon atoms. Sulfuric acid ester salts of primary alcohols, Sulfuric acid ester salts of ethoxylated linear or branched primary or secondary alcohols having 8 to 20 carbon atoms, alkylbenzene sulfonates having 8 to 16 carbon atoms in alkyl groups, alkanes One or more selected from sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts and the like can be mentioned. Suitable salts of these anionic surfactants are Na, K and NH ₄ .
The component (a) is contained in the composition in an amount of 15 to 50% by weight, preferably 20 to 40%.
% By weight. Good detergency is exhibited in the compounding amount of this range.

<(B) Carboxybetaine type surfactant>
The carboxybetaine type surfactant used in the present invention is represented by the above general formula (I). General formula (I)
In, when R ₁ has 12 to 14 carbon atoms, the cleaning effect is highest. When R ₂ and R ₃ are methyl, the cleaning effect is highest.

In the present invention, the component (b), a carboxybetaine type surfactant, is incorporated in the composition in an amount of 1 to 20% by weight, preferably 2 to 10% by weight. Good cleaning power is exhibited within this range.

In the present invention, the weight ratio of the above component (a) and component (b) is important. That is, the weight ratio of (b) / (a) is 1/100 to 100/100, preferably 3/100 to 50/100.
It is. If the weight ratio of (b) / (a) deviates from this range, the detergency will decrease.

The carboxybetaine type surfactant as the component (b) has long been well known as a surfactant used in shampoos and liquid detergents, and many patent applications have been filed. For example, Japanese Patent Publication No. 48-8243 and Japanese Patent Publication No. 48-1736.
No. 3 and others are used for shampoo.
JP-B-51-39964 and the like disclose the use of liquid cleaning agents. However, it has not been known at all until now that, in a combined use system with an anionic surfactant, by setting the weight ratio of the both to a specific range, the detergency of the high-density granular detergent is remarkably improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the above (a) and
A high-density granular detergent composition in which detergency is further improved by further adding the following aluminosilicate, crystalline silicate and other alkali agents, biodegradable organic builders, polycarboxylates, etc. to the surfactant (b) The thing is obtained.

<Aluminosilicate> As the aluminosilicate, either amorphous or crystalline can be used. As the amorphous aluminosilicate, those containing 30% by weight or more, preferably 40% by weight or more of silicon as SiO ₂ are good,
Also, if the pH of the 5% dispersion is 9 or higher,
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) (In the formula, M represents 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 and c are arbitrary positive numbers. ] In particular, the following general formula (ii) Na ₂ O ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (ii) [where b is 1.8 to 3.2 and c is a number from 1 to 6] Represents ]
Is preferably represented by

A method for producing such an amorphous aluminosilicate will be briefly described. First, the molar ratio of SiO ₂ and M ₂ O (M means an alkali metal) is SiO ₂ / M ₂ O = 1.0 to 4.0, and H ₂
In an aqueous solution of an alkali metal silicate having a molar ratio of O and M ₂ O of H ₂ O / M ₂ O = 12 to 200, the molar ratio of M ₂ O and Al ₂ O ₃ is M ₂ O / A.
a l ₂ O ₃ = 1.0~2.0, the molar ratio of between H ₂ O and M ₂ O is H ₂ O / M
_An aqueous solution of a low-alkali alkali metal aluminate having an amount of ₂ O = 6.0 to 500 is added under strong stirring at a temperature of 15 to 60 ° C, preferably 30 to 50 ° C. Further, an aqueous solution of an alkali metal silicate may be added to the aqueous solution of an alkali metal aluminate. Then, the white precipitate slurry formed was mixed with 70-100
It can be advantageously obtained by heat treatment at a temperature of 90 ° C., preferably 90 to 100 ° C. for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. By this method, ion exchange capacity 100 CaCO ₃ mg / g or more, oil absorption capacity
An amorphous aluminosilicate of 200 ml / 100 g or more can be easily obtained.

The pH of a 5% dispersion of amorphous aluminosilicate is measured according to JIS K 6220. That is, about 5 g of a sample is weighed and placed in a hard Erlenmeyer flask, and water containing no carbonic acid.
Add 100ml, stopper and shake for 5 minutes. The liquid after shaking was used as the test liquid and the glass electrode method (JIS Z 8802.
Measure pH according to 2.3). By selecting an amorphous aluminosilicate having a pH of 9.0 or more in the 5% dispersion, it is possible to obtain a high-density detergent composition whose solubility does not deteriorate when stored under high humidity conditions.

Further, if the alkalinity of the detergent is very high or the storage conditions are very harsh, 2% Na is more severe.
It is preferable to select an amorphous aluminosilicate that satisfies the condition that the dissolution amount in an OH aqueous solution is 0.5 g or less. That is, 10 g of amorphous aluminosilicate is mixed with 100 ml of 2% NaOH aqueous solution.
And stirred for 16 hours at a constant temperature of 25 ° C. to remove SiO ₂ from the filtrate.
(For colorimetry, see Oil Chemistry, Vol. 25, p. 156, 1976), the amount of which is less than 0.5 g as an amorphous aluminosilicate.

The crystalline aluminosilicate 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) [In the formula, M represents an alkali metal atom, a ', b', w represents a molar ratio of each component, and generally 0.7 ≤ a '≤ 1.5, 0.8 ≤ b'<
6 and w are arbitrary positive numbers. ], And
Among them, the following general formula (iv) Ma 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), a synthetic zeolite having an average primary particle diameter of 0.1 to 10 μm represented by A-type, X-type and P-type zeolite is 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 1 to 60% by weight, preferably 8 to 30% by weight. If the amount of the aluminosilicate is out of this range, the detergency will decrease.

<Alkali agent> The composition of the present invention may contain an alkali agent such as an inorganic alkali metal salt or polyphosphate.

As the inorganic alkali metal salt and / or polyphosphate salt, the following (1) to (2) can be used.

(1) Inorganic alkali metal salts sodium carbonate, potassium carbonate, sodium silicate [(Na ₂
O) _m (SiO ₂ ) _n , where m is 1 to 5 and n is 1 to 3. ], Sodium bicarbonate, potassium bicarbonate, sodium sulfite, potassium sulfite, sodium sesquicarbonate, potassium sesquicarbonate, and crystalline silicate.

The crystalline silicate used in the present invention is silicic acid.
Alkali metal salts of (SiO ₂ ) are preferable, and among them, those in which SiO ₂ / M ₂ O (where M represents an alkali metal) of the alkali metal silicate is 0.5 to 2.6 are preferably used. The conventionally known crystalline silicate has a SiO ₂ / M ₂ O content of 1.9 to 4.0.
However, if this ratio exceeds 2.6, it may not be suitable for the formulation of the high-density detergent which is the subject of the present invention.

The crystalline silicate suitable for use 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 Shows one or a combination of two or more elements selected from the group IIa, IIb, IIIa, IVa and VIII elements 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 above general formula (II) will be described. In the general formula (II), M
Is selected from Group Ia elements of the Periodic Table, and as Group Ia elements,
Na, K, etc. are mentioned. These may be alone or for example Na
₂ O and K ₂ O may be mixed to form the M ₂ O component.

Me is a IIa group element, IIb group 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 Mg and Ca are preferable from the viewpoint of resources and safety. Further, it may be mixed alone or two or more, for example MgO, CaO or 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. When z / x is less than 0.01, the water resistance is insufficient, and when 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,
When x (M ₂ O) is, for example, x ′ (Na ₂ O) · x ″ (K ₂ O) · as described above, 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. Further, n / m indicates the number of oxygen ions coordinated to the element, and is substantially 0.5, 1.0, 1.
5 or 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 as follows. The above raw material components are mixed in a predetermined quantitative ratio so that the desired x, y, z values of the crystalline silicate are obtained. 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 crystalline silicate represented by the general formula (II) thus obtained is 11% in 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 the alkaline ability and the alkaline buffering effect, and further has the ion exchange ability. Therefore, the washing conditions described above can be suitably adjusted by appropriately adjusting the blending amount.

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. When the average particle size exceeds 100 μm, the rate of ion exchange tends to be slow, resulting in deterioration of detergency. Further, if it is less than 0.1 μm, the hygroscopicity and CO ₂ absorbing property 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 pulverizing with a pulverizer such as a vibration mill, a hammer mill, a ball mill or a roller mill. For example, it can be easily obtained by crushing with an HB-O type vibration mill (manufactured by Chuo Kakoki Co., Ltd.).

Next, the crystalline silicate represented by the general formula (III) will be described. This crystalline silicate is represented by the general formula (III): M ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (III) wherein M represents an alkali metal and x ′ = 1.5 to 2.6 , Y '
= 0 to 20. Is represented by the general formula (I
It is preferable that x ′ and y ′ in 1.7) are 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 alkali ability and an alkali 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) can be obtained, for example, from Hoechst under the trade name “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 size 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) may be used alone or in combination of two or more kinds.

In the present invention, the crystalline silicate is blended in the composition in an amount of 1 to 40% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight, from the viewpoints of detergency and powder physical properties. .

(2) Polyphosphate salts Polyphosphate salts such as orthophosphate salts, metaphosphate salts, pyrophosphate salts, tripolyphosphate salts, and hexametaphosphate salts can be used. As the salt, H 2, Na and K are generally used.

An alkali agent such as an alkali metal salt or polyphosphate is preferably contained in the composition in an amount of 5 to 60% by weight, more preferably 10 to 40% by weight.

Of the alkaline agents contained in the composition, the crystalline silicate is preferably contained in an amount of 10 to 100% by weight, more preferably 50 to 80% by weight.

<Organic builder with good biodegradability> 1) below
The organic builder of ~ 2) has good performance as a builder,
It also has good biodegradability and is suitable as a builder to be incorporated into the high-density granular detergent composition of the present invention.

[0046]

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The builder of 1) to 2) has 0.5 to 20% in the composition.
%, Preferably 1.0 to 10% by weight.

<Polycarboxylate> Molecular weight of several hundreds
Polycarboxylates such as 100,000 copolymers represented by the following formula (IV) and / or homopolymers represented by the formula (V) are also preferably used.

[0049]

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(In the formula, Z is a 1-8 olefin, acrylic acid, methacrylic acid, itaconic acid, methacryl sulfonic acid, or the like (anhydrous) maleic acid or a monomer copolymerizable with the maleic acid salt and (anhydrous) maleic acid). A salt of a copolymer of an acid or a maleate salt, m is a value such that the molecular weight of the copolymer is several hundreds to 100,000, and M is Na, K, NH ₄ , or H.)

[0051]

[Chemical 6]

(In the formula, P is a homopolymerizable monomer, examples of which include acrylic acid, methacrylic acid, and maleic acid. M'is a value such that the homopolymer has a molecular weight of several hundred to 100,000. The salt of the homopolymer is Na, K 2, NH _4, etc.) The compounding amount of the copolymer of the formula (IV) and / or the homopolymer of the formula (V) is 1 with respect to 100 parts by weight of the detergent composition. -8 parts by weight, preferably 2-6 parts by weight. Among these polycarboxylates, salts of acrylic acid-maleic acid copolymers and polyacrylic acid (Na, K, N, respectively)
H ₄ ) is particularly good. The molecular weight is preferably from 1,000 to 80,000.

The following 1) to 3) may be blended as an organic builder. 1) Salts of phosphonic acids such as ethane-1,1-diphosphonic acid and ethane-1,2-triphosphonic acid 2) Polyelectrolytes such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose and polyaspartic acid 3) Organic acid salts such as diglycolic acid, oxydisuccinic acid, etc. Furthermore, the following components can be added as components other than the above. Examples of the bleaching agents include sodium percarbonate, sodium perborate (preferably monohydrate), sodium sulfate hydrogen peroxide adduct, and the like, and sodium percarbonate is particularly preferable.

As the bleach activator, tetraacetylethylenediamine, acetoxybenzene sulfonate, organic peracids described in JP-A-59-22999, JP-A-63-258447 and JP-A-6-316700. Examples thereof include a precursor or a metal catalyst obtained by stabilizing a transition metal with a sequestering agent.

Enzymes (which are enzymes that inherently perform an enzyme action during the washing step) are classified according to the reactivity of the enzyme, such as 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, carbohydrases, nucleases, cellulases and amylases.

Specific examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sputiricin, BPN, papain, promerin, carboxypeptidase A and B, aminopeptidase, aspergiropeptidase A and B. , Commercially available products such as Sabinase, Alcalase (Novo Industry Co., Ltd.), API 21 (Showa Denko KK), Maxacar (Gist Procades Co., Ltd.), Protease K-14 or K-16 described in JP-A-5-43892. There is.

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

As the lipase, for example, a commercially available lipase such as ribolase (Novo Industry) can be used.

Specific examples of carbohydrase include cellulase, maltase, saccharase, amylase, pectinase, 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 needed. For example, those having the structures of the following formulas (i) and (ii) are recommended.

[0063]

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(In the formula, D ₁ represents a blue to purple monoazo, disazo or anthraquinone dye residue, and X ₁ and Y ₁
Is a hydroxyl group; an aliphatic amino group which may be substituted with an amino group, a hydroxyl group, a sulfonic acid group, a carboxylic acid group or an alkoxy group; a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxylic acid group, a lower alkyl group or a lower alkoxy Represents an aromatic amino group or a cycloaliphatic amino group which may be substituted with a group, and R represents a hydrogen atom or a lower alkyl group. However, when R represents a hydrogen atom, X ₁ and Y ₁ simultaneously represent a hydroxyl group or an alkanolamino group, and either _one of X ₁ and Y ₁ is a hydroxyl group,
Except when the other is an alkanolamino group. n is 2
Represents the above integer. )

[0065]

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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 are the same or different alkanolamino groups or hydroxyl groups. Represents.).

Examples of the anti-caking agent include paratoluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, fine powder 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.

As the antioxidant, tert-butylhydroxytoluene, 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 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 the fluorescent dye, 4,4'-bis- (2-sulfostyryl) -biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) ) 0.1 to 1% by weight of the naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative, bis (triazinylamino) stilbene disulfonic acid derivative in the composition. Can be included.

As the fragrance, it is possible to use the fragrances conventionally blended in detergents, for example, the fragrances described in JP-A-63-101496.

The high-density detergent composition of the present invention is a powder or granular composition, but the production method is not particularly limited, and a conventionally known method can be used. 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.
JP-A 61-69899, JP-A 61-69900, JP-A 2
-222498, JP-A-2-222499, JP-A-3-222498
No. 33199, JP-A-5-86400, JP-A-5-20
The method described in JP-A-9200 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 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, granulation, or dry blending.

The average particle size of the anionic high-density granular detergent composition of the present invention is 200 to 10 in order to obtain preferable powder physical properties.
It is desirable that the thickness is 00 μm, particularly 200 to 600 μm. The bulk density of the detergent composition of the present invention is 0.5 to 1.2 g / ml,
It is preferably 0.6 to 1.0 g / ml.

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

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, a carboxybetaine type surfactant which is excellent in biodegradability and safety is mixed with an anionic surfactant in an appropriate amount so that the detergency is further improved. A granular detergent composition is obtained.

[0075]

EXAMPLES The present invention will be described below in detail with reference to 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 method. Zeolite
1.0kg, AS 2.62kg, AM 0.5kg, soda ash 0.75kg, PEG
0.1 kg and fluorescent dye (4,4'-bis- (2-sulfostyryl) -biphenyl salt) 0.05 kg to prepare a slurry with a water content of 50% by weight, and spray-dry it to obtain a high-speed powder. Put into a mixer (stirring granulator, Fukae Industry Co., Ltd.), add 0.25 kg of zeolite, 0.88 kg of carboxybetaine (CB-1), 2.0 kg of silicate (II) to granulate,
Further, 0.25 kg of zeolite was added for granulation, and the resulting particles were dry-mixed with 0.5 kg of the remaining zeolite and 0.1 kg of enzyme to obtain a high-density granular detergent composition (average particle size 450
μm, bulk density 780 g / liter). With respect to the other products of the present invention and comparative products shown in Tables 1 to 4, high-density granular detergent compositions were prepared in accordance with the above-mentioned schemes at respective compounding ratios.

(2) A detergency test was performed on the obtained high-density granular detergent composition by the following method. Table 1 shows the results.
-4 are shown. <Detergency test> (Preparation of artificially contaminated cloth) An artificially contaminated cloth was prepared by adhering an artificially contaminated liquid having the following composition to the cloth. The artificial contaminant was attached to the cloth by using a gravure roll coater. The process of adhering the artificially contaminated liquid to the cloth to make the artificially contaminated cloth includes a gravure roll cell capacity of 58 cm ³ / m ² , a coating speed of 1.0 m / min,
The drying was performed at a drying speed of 100 ° C. for 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.

(Washing conditions and evaluation method) Five pieces of 10 cm x 10 cm artificially contaminated cloth prepared as described above were put in 1 liter of an aqueous detergent solution for evaluation, and washed with a tergotometer at 100 rpm. The washing conditions are as follows.・ Washing conditions Washing time 10 minutes Detergent concentration 0.067% Water hardness 4 ° DH Water temperature 20 ° C Rinse with tap water for 5 minutes Detergency is the reflectance at 550 nm of the original cloth before and after cleaning. It was measured with a meter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the following formula, and the average value of the five measured values was shown as the cleaning power.

[0079]

[Equation 1]

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

-AS: Alkyl (C ₁₄ ) sulfate Na salt-LAS: Linear alkyl (C ₁₂ ) benzenesulfonic acid Na salt-FA: Partic acid Na salt-CB-1: Dodecyldimethylcarboxybetaine-CB-2 : Tetradecyldimethylcarboxybetaine-Zeolite (Crystalline aluminosilicate: Composition M ₂ O ・ Al ₂ O
_{3 · 2SiO 2 · 2H 2 O} , an average particle diameter of 2 [mu] m, the ion exchange capacity 2
90 CaCO ₃ mg / g, M is Na, K) ・ Silicate (II): Composition M ₂ O ・ 1.8 SiO ₂・ 0.02 M ' ₂ O (where M: Na, K, K / Na = 0.03, M '＝ Ca, Mg, Mg / Ca ＝
0.01), ion exchange capacity 290 CaCO ₃ mg / g, average particle size
30 μm [Crystalline silicate represented by general formula (II)]-Silicate (III): Composition M ₂ O · 2 SiO ₂ , ion-exchange capacity 2
24 CaCO ₃ mg / g, average particle diameter 30 μm [crystalline silicate represented by general formula (III)]-AE-1: polyoxyethylene (8.0 mol) dodecyl ether (HLB 13.1) -AM: acrylic acid / Na salt of maleic acid (molar ratio 7/3) copolymer, average molecular weight 70,000 ・ PA: Na salt of polyacrylic acid, average molecular weight 8000 ・ HIDS: Hydroxyiminodisuccinic acid Na salt [R 2 in the above formula] H] ASDA: aspartic acid diacetic acid Na salt [in the above formula 1)
R = H] ・ Common component: PEG (polyethylene glycol having an average molecular weight of 7,000) 1%, enzyme [API-21H (Showa Denko KK),
Lipolase 100T (Novo Nordisk), Cellzyme
0.1T (manufactured by Novo Nordisk) and Termamill 60T (manufactured by Novo Nordisk) mixed at 2: 1: 1: 1]
1%, fluorescent dye 0.5%, and mirabilite, which were adjusted to 100% with mirabilite.

Example 2 (1) Preparation of High Density Granular Detergent Composition Inventive product 1 in Table 5 was prepared by the following method. Zeolite
1.0kg, AS 2.62kg, AM 0.5kg, soda ash 1.25kg, PEG
0.1 kg, fluorescent dye (4,4'-bis- (2-sulfostyryl) -biphenyl salt) 0.05 kg, carboxybetaine (CB-
A slurry having a water content of 50% by weight was prepared from 0.88 kg of the aqueous solution (1) (as CB-1) and spray-dried to obtain a high-speed mixer (stirring granulator, Fukae Industry Co., Ltd.). ), 0.5 kg of zeolite, silicate (II) 2.0
Granulate by adding kg, and further granulate by adding 0.25 kg of zeolite, and the remaining particles 0.25 kg of zeolite and enzyme 0.1
A high-density granular detergent composition was obtained by dry mixing kg (average particle size: 490 μm, bulk density: 760 g / liter).

With respect to the other products of the present invention and comparative products shown in Table 5, high-density granular detergent compositions were prepared according to the above-mentioned schemes in the respective mixing ratios. However, the ASDA compounded in the product 3 of the present invention was added to the slurry before spray drying. Further, in Comparative Product 4, a porous silica compound was added to a high-speed mixer in the same manner as silicate, mirabilite, etc. to granulate, and a predetermined amount of AE-1 heated to 70 ° C was added to granulate, and zeolite was added. Granulation, and the remaining zeolite was further added to granulate to obtain a high-density granular detergent composition.

(2) A detergency test was performed on the obtained high-density granular detergent composition by the following method. The results are shown in Table 5.
It was shown to. <Detergency test> (Preparation of artificially contaminated cloth) The same artificially contaminated liquid as in Example 1 was adhered to the cloth to prepare an artificially contaminated cloth. The artificial contaminant was attached to the cloth by using a gravure roll coater. The process of making the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth is the gravure roll cell capacity of 58 cm ³ / m ² and the coating speed of 1.0 m / mi.
n., drying speed 100 ° C., drying time 1 minute. The cloth used was a cotton gold cloth 2003 (manufactured by Tanito Shoten).

[0088]

[Equation 2]

[0089]

[Table 5]

(Note) The symbols in Table 5 are the same as above.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location (C11D 10/02 1:02 1:90 3:08 3:33) (72) Inventor Noboru Moriyama 1334 Minato Minato, Wakayama, Wakayama Kao Corporation Research Center

Claims (8)

[Claims] (A) 15-50% by weight of anionic surfactant (b) 1.0-20% by weight of carboxybetaine type surfactant represented by the following general formula: (Wherein R ₁ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₂ and R ₃ are alkyl groups or alkenyl groups having 1 to ₃ carbon atoms, or H), and (b) / (A) weight ratio is 1/100 to 100/100 and bulk density is 0.5 to 1.2
High density granular detergent composition of g / ml. 2. The high-density granular detergent composition according to claim 1, which contains 1 to 60% by weight of aluminosilicate. 3. The high-density granular detergent composition according to claim 1, which contains 1 to 40% by weight of the crystalline silicate of the following formula (II) or / and (III). x (M ₂ O) ・ y (SiO ₂ ) ・ z (Me _m O _n ) ・ w (H ₂ O) (II) (In the formula, M represents a group Ia element of the periodic table, and Me represents a group IIa. Element, Group IIb element, Group IIIa element, Group IVa element or VIII
One or two or more kinds selected from group elements are shown, y / x = 0.5 to 2.6, z / x = 0.01 to 1.0, w = 0 to 2
0, n / m = 0.5 to 2.0. ) M ₂ O ・ x '(SiO ₂ ) ・ y' (H ₂ O) (III) (In the formula, M represents an alkali metal, x '= 1.5 to 2.6, y'
= 0 to 20. ) 4. An organic builder represented by the following formulas 1) to 2)
The high-density granular detergent composition according to any one of claims 1 to 3, which comprises 0.5 to 20% by weight. Embedded image 5. The anionic surfactant (a) has 10 to 10 carbon atoms.
18 higher fatty acid salts, 1 straight or branched chain with 10 to 18 carbon atoms
Sulfate ester salts of secondary or secondary alcohols with 8 to 20 carbon atoms
Alcohol ethoxylate sulfate ester salt,
One selected from alkylbenzene sulfonates having 8 to 16 carbon atoms in the alkyl group, alkane sulfonates (SAS), α-olefin sulfonates, α-sulfo fatty acid salts and α-sulfo fatty acid alkyl ester salts, or The high-density granular detergent composition according to any one of claims 1 to 4, which is two or more kinds. 6. The high-density granular detergent composition according to claim 1, which contains 1 to 15% by weight of a nonionic surfactant. 7. The nonionic surfactant is polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol ether, polyoxyethylene polyoxypropylene block polymer and alkanoyl N-methyl. The high-density granular detergent composition according to claim 6, which is one kind or two or more kinds selected from glucamine. 8. The high-density granular detergent composition according to claim 1, which contains a polycarboxylate having an average molecular weight of 1,000 to 100,000.