JPH09241677A - High-density granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing an anionic surfactant and a specific amidoamine oxide-type surfactant at specific ratios, having excellent biodegradability and safety and exhibiting extremely high detergent power. SOLUTION: This detergent composition contains (A) 10-50wt.% of an anionic surfactant (e.g. an alkylbenzenesulfonic acid salt having an 8-16C alkyl group) and (B) 1-20wt.% of an amidoamine oxide-type surfactant of formula I (R1 is a 10-20C alkyl or alkenyl; R2 and R3 are each H, a 1-3C alkyl, etc.; R4 is H, a 1-5C alkyl, etc.; (n) is 1-5) at a weight ratio (B/A) of (1-100)/100. The bulk density of the composition is 0.6-1.2g/mL. A composition having further improved detergent power can be produced by compounding the composition further with 1-60wt.% of an aluminosilicate, 5-30wt.% of a crystalline silicate of formula II (M is an element of the group Ia of the periodic table; Mc is an element of the group IIa, IIb, etc., of the periodic table; y/x is 0.5-2.6; z/x is 0.01-1; (w) is 0-20; n/m is 0.5-2), etc.

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 incorporating an amide oxide type surfactant excellent in biodegradability and safety into an anionic surfactant in an appropriate amount.

[0002]

2. Description of the Related Art Detergents for clothing solubilize stains or dissolve from fibers into washing liquids.
To remove surfactants that disperse, alkaline agents that accelerate the decomposition and solubilization (emulsification) of soil, polymer compounds that disperse soil, and calcium and magnesium that reduce the ability of surfactants from the washing liquid. It is basically composed of a metal sequestering agent. 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 used mainly for anionic properties, alkylbenzene sulfonate having 10 to 16 carbon atoms, sulfuric acid ester salt of higher alcohol having 10 to 18 carbon atoms, α-olefin sulfonate, α
-Sulfo higher fatty acid ester salts, alkane sulfonates (SAS) and the like, and as the surfactants mainly used for those mainly having nonionic properties, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether And so on. Examples of these are, for example, Japanese Patent Publication No. 64-10039, Japanese Patent Publication No. 43119, and Japanese Patent Publication No. 5119.
-66440, JP-A-4-339898, JP-A-5-5100,
There are JP-A-6-9999 and JP-A-6-10,000.

The high density, compactness and miniaturization of detergents have been advanced 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.

Amidoamine oxide type surfactants are
It has good biodegradability and excellent safety, but the optimum formulation for high-density detergent has not yet been known. From such a situation, the object of the present invention is to mix an amidoamine oxide type surfactant with an anionic surfactant in an appropriate amount.
An object of the present invention is to provide a high-density granular detergent having higher detergency.

[0006]

Means for Solving the Problems As a result of various investigations by the present inventors, when the anionic surfactant is mainly used as the surfactant and a specific amidoamine oxide is used at a specific compounding ratio, the detergency is remarkably increased. I found it to be high.

That is, the present invention comprises (a) 10 to 50% by weight of anionic surfactant (b) 1.0 to 20% by weight of amidoamine oxide type surfactant represented by the following general formula, and (b) / (a) Weight ratio is 1/100 to 100/100 and bulk density is 0.6 to 1.2g
/ Ml high density granular detergent composition.

[0008]

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(In the formula, R ₁ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₂ and R ₃ are H or an alkyl group or alkenyl group having 1 to 3 carbon atoms, and R ₄ is H or 1 carbon atom. To 5 are alkyl groups or alkenyl groups, and n is 1 to 5.) The high-density granular detergent composition of the present invention will be described below.

(A) Anionic Surfactant As the anionic surfactant used in the present invention, a higher fatty acid salt having 8 to 18 carbon atoms and a linear or branched primary or secondary alcohol having 8 to 18 carbon atoms. Sulfate ester salt, C8-C20 straight chain or branched chain primary or secondary alcohol ethoxylate sulfate salt, alkyl group having 8 to 16 carbon atoms, alkylbenzene sulfonate, alkane sulfonic acid One or more selected from salts (SAS), α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt and the like. Salts of these anionic surfactants include Na, K, NH ₄
Is suitable. The component (a) is incorporated in the composition in an amount of 15 to 50% by weight, preferably 20 to 40% by weight.

(B) Amidoamine Oxide Surfactant The amidoamine oxide surfactant used in the present invention is represented by the general formula (1). R ₂ and R ₃ are most effective when they are methyl. R ₁ is most effective when it has 12 to 14 carbon atoms.

In the present invention, the component (b), an amidoamine oxide type surfactant, is incorporated in the composition in an amount of 1 to 20% by weight, preferably 2 to 10% by weight. If it deviates from this range, the detergency will decrease.

In the present invention, the weight ratio of (b) / (a) is 1/100 to 100/100, preferably 3/100 to 50 /.
It is 100. If the weight ratio of (b) / (a) deviates from this range, the detergency will decrease. The amidoamine oxide type surfactant as the component (b) has long been well known as a shampoo and a liquid detergent, and many patents have been applied for. For example, JP-A-47-34604, JP-A-61-283695
And JP-A-62-20596 and JP-A-5-170628.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION If the surfactants of (a) and (b) above are further blended with the following aluminosilicate, crystalline silicate, biodegradable organic builder, polycarboxylate, etc. A high density granular detergent composition with improved power 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) (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, 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 ₂
An aqueous solution of a low alkali metal alkali aluminate having an O = 6.0-500 is added under strong stirring at a temperature of 15-60 ° C, preferably 30-50 ° 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 was then heated to 70-100 ° C.
It can be advantageously obtained by performing a heat treatment at a temperature of preferably 90 to 100 ° C. for 10 minutes to 10 hours, 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 200 ml
/ 100 g or more of an amorphous aluminosilicate 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, when the alkalinity of the detergent is very high or the storage conditions are very severe, the more severe 2% Na
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 a 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, 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 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.

<Crystalline Silicate> 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 general formula (II) will be described.

In the general formula (II), M is Ia of the periodic table.
Group Ia elements are selected from the group Ia elements, such as 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 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. These may be used alone or as a mixture of two or more. For example, MgO 2, CaO 2
Etc. 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
It is _composed of three components, M ₂ O, SiO ₂ and Me _{m On} . Therefore, in order to produce the crystalline silicate represented by the general formula (II), each component is required as a raw material, but 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, M ₂ O
The raw material _{components, NaOH, KOH, Na 2 CO} 3, K 2 CO 3, Na
Etc. ₂ SO ₄ is, as a raw material of Me _m O _n component, CaCO _3, MgC
O 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 raw material components in a predetermined quantitative ratio so that x, y, and z values of the desired crystalline silicate can be 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) is
Preferably, the average particle size is 0.1 to 100 μm,
More preferably, it is 1 to 60 μm. Average particle size 100 μm
When it exceeds, the rate of onset of ion exchange tends to be slow, leading to a decrease in 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 crushing with a crusher 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 above 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 mixed in the composition in an amount of 0 to 40% by weight, preferably 5 to 35% by weight. If the compounding amount of the crystalline silicate is small, the detergency is lowered, and if it exceeds 40%, the hygroscopicity is increased and the physical properties of the powder such as caking are deteriorated.

<Alkaline agent> As the alkaline agent, in addition to the above-mentioned crystalline silicate, sodium carbonate, potassium carbonate,
Sodium silicate, sodium bicarbonate, potassium bicarbonate,
Sodium sulfite, potassium sulfite, sodium sesquicarbonate, sodium orthophosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and the like can be used. Of the alkaline agents contained in the composition, the crystalline silicate content is 0 to 100% by weight, preferably 20 to 100% by weight, more preferably 60 to 90% by weight.
It is desirable to be included.

<Organic Builder Having Good Biodegradability> As an organic builder having good biodegradability, the following builder is blended to obtain a detergent composition having further excellent cleaning performance.

[0040]

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The builders (1) and (2) have 0.5% by weight in the composition.
-30% by weight, preferably 1.0-10% by weight.

<Nonionic Surfactant> Polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester,
One or more compounds selected from polyoxyethylene polyoxypropylene block polymers and alkanoyl N-methylglucamine. HL among them
Polyoxyethylene alkyl ethers having a B value of 10.5-15.0 are particularly preferred. The nonionic surfactant is preferably incorporated in the composition in an amount of 1 to 15% by weight.

<Polycarboxylate> Molecular weight of several hundreds
100,000 polycarboxylates such as copolymers of formula (IV) and / or homopolymers of formula (V)

[0044]

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(In the formula, Z is 1 to 8 olefin, acrylic acid, methacrylic acid, itaconic acid, methallyl sulfonic acid, etc.) (maleic anhydride) or a monomer copolymerizable with maleic acid and (anhydrous) maleic acid. Or a salt of a copolymer of maleic acid salt, m is a value such that the molecular weight of the copolymer is several hundred to 100,000, and M is Na, K or NH _3. )

[0046]

[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. Acrylic acid among these polycarboxylate - salts of maleic acid copolymers and salts of polyacrylic acid (each, Na, K, NH ₄₎
Is particularly excellent. The molecular weight is preferably 1,000 to 80,000.

As organic builders, the following 1) to 3)
May be blended.

1) ethane-1,1-diphosphonic acid, ethane-
Salts of phosphonic acids such as 1,2-triphosphone 2) Polymer electrolytes such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, polyaspartic acid 3) Organic acid salts such as diglycolic acid and oxydisuccinic acid The following components can be blended as components.

Examples of the bleaching agent 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 enzymatic 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 esterases include gastric lipases, buncreatic lipases, plant lipases,
There are phospholipases, cholinesterases and phosphotases.

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

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

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

As the 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 blended as required. For example, those having the structures of the following formulas (i) and (ii) are recommended.

[0060]

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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 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. )

[0062]

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(In the formula, 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. 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 antioxidants, tertiary butyl hydroxytoluene, 4,4'-butylidene bis- (6-tert-butyl-3-methylphenol), 2,2'-butylidene bis-
(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) ) One or more of a naphthothiazole derivative, a 4,4'-bis (triazol-2-yl) stilbene derivative, and a bis (triazinylamino) stilbene disulfonic acid derivative are contained in the composition in an amount of 0 to 1% by weight. Can be included.

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

The high-density detergent composition of the present invention is a powder or granular composition, but the production method thereof is not particularly limited, and conventionally known methods 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 component (B), amidoamine oxide, may be added before the spray-drying step or after that step.

The nonionic high-density granular detergent composition of the present invention has an average particle size of 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 / c.
m ^3, preferably about 0.6~1.0 g / cm ^3.

The detergent composition of the present invention is used in a concentration suitable for each washing depending on a washing method such as washing with a washing machine and washing with soaking, and the amount of clothes and water, the degree of dirt, the method of using a machine and the like. 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.

[0071]

According to the present invention, a high-density granular detergent composition having excellent detergency by using an amidoamine oxide type surfactant having excellent biodegradability and safety as a main component of the surfactant. The thing is obtained.

[0072]

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 <Preparation of High Density Granular Detergent Composition> (1) The product 1 of the present invention in Table 1 was prepared by the following method. Zeolite 0.5kg, AS2.62kg, AM 0.5kg, soda ash 1.25k
A powder obtained by preparing a slurry having a water content of 50% by weight from g, PEG 0.1 kg, and a fluorescent dye (4,4′-bis- (2-sulfostyryl) -biphenyl salt) 0.05 kg, and spray-drying the slurry. Was put into a high-speed mixer (stirring granulator, Fukae Kogyo Co., Ltd.), zeolite 0.5 kg, amidoamine oxide (AO-1) 0.88 kg, silicate (II) 2.0 kg
Granulate by adding 0.5 kg of zeolite, and granulate by adding 0.5 kg of zeolite.
A high-density granular detergent composition was obtained by dry-mixing kg (average particle size 420 μm, bulk density 800 g / liter).

Other products of the present invention listed in Tables 1 to 3,
For comparative products, high-density granular detergent compositions were prepared according to the above-mentioned schemes at the respective mixing ratios. When the content of zeolite was small as in the case of the products 18 and 19 of the present invention, it was not added to the slurry before spray drying and was used by dividing it into the subsequent steps.

(2) The product 27 of the present invention was prepared by the following method.
Zeolite 1.0kg, AS 2.62kg, AM 0.5kg, soda ash 1.25kg, PEG 0.1kg, fluorescent dye (4,4'-bis-
(2-sulfostyryl) -biphenyl salt) 0.05 kg, an aqueous solution of amidoamine oxide (AO-1) 0.88 kg (AO
-1) to prepare a slurry having a water content of 50% by weight,
The powder obtained by spray-drying it is put into a high-speed mixer (stirring granulator, Fukae Industry Co., Ltd.),
Granulate by adding 0.5 kg of zeolite and 2.0 kg of silicate (II), further granulate by adding 0.25 kg of zeolite, and dry mix the remaining 0.25 kg of zeolite and 0.1 kg of enzyme with the obtained particles to obtain a high mixture. A granular detergent composition was obtained (average particle size
490 μm, bulk density 760 g / liter).

Other products 28 to 30 of the present invention in Table 4 and comparative product 7
Also for 9 to 9, high-density granular detergent compositions were prepared in accordance with the above-mentioned schemes at respective mixing ratios. However, this invention product 29
Was added to the slurry prior to spray drying. Further, in Comparative product 10, 1.0 kg of 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 to produce a porous product. 0.5 kg of a hydrophobic silica compound was added for granulation, and 0.5 kg of the remaining porous silica compound was further added for granulation to obtain a high-density granular detergent composition. Further, in Comparative product 10, since the amount of zeolite contained was small, zeolite was not added before spray drying, and was used by dividing it into the subsequent steps.

(3) A detergency test was conducted 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 making the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth is as follows: cell volume of the gravure roll 58 cm ³ / m ² , coating speed 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 condition Washing time 10 minutes Detergent concentration 0.067% Water hardness 4 ° DH Water temperature 20 ° C Rinse 5 minutes with tap water Detergency is the reflectance at 550 nm of the original cloth before contamination and the contaminated cloth before and after washing. 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 ester Na
Salts - LAS: linear alkyl (C ₁₂₎ benzene sulfonic acid Na salt-FA: palmitic acid Na salt-AO-1: lauroyl amidopropyl dimethylamine oxide · AO-2: Millis Ciro yl amidopropyl dimethylamine oxide, zeolites ( Crystalline aluminosilicate: composition M ₂ O ・ Al ₂ O
₃・ 2SiO ₂・ 2H ₂ O, average particle size 2 μm, 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'O (where M: Na, K, K / Na = 0.03, M '= Ca, Mg, Mg / Ca = 0.0
1), 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 · 2SiO ₂ , ion exchange capacity 22
4 CaCO ₃ mg / g, average particle diameter 30 μm (crystalline silicate represented by general formula (III))-AE-1: nonionic activator, polyoxyethylene 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 derivative ・ ASDA: Aspartic acid diacetic acid derivative ・ PEG: Polyethylene glycol with an average molecular weight of 7,000 ・ Common component: PEG 1%, enzyme [API-21H (Showa Denko
Ltd.), Lipolase 100T (Novo Nordisk),
Cellzyme 0.1T (Novo Nordisk), Termamill
A mixture of 60T (manufactured by Novo Nordisk Co., Ltd.) in a ratio of 2: 1: 1: 1] 1%, fluorescent dye 0.5% and mirabilite, and the total amount was adjusted to 100% with mirabilite.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takaya Sakai 1334 Kao Co., Ltd., Wakayama City, Wakayama Prefecture Kao Co., Ltd. (72) Inventor Masaaki Yamamura 1334 Minato Minato, Wakayama City, Wakayama Prefecture (72) Inventor, Kao Co., Ltd. Noboru Moriyama 1334 Minato Minato, Wakayama, Wakayama Prefecture Kao Corporation Research Laboratory

Claims (8)

[Claims] 1. An (a) anionic surfactant 10 to 50% by weight (b) 1.0 to 20% by weight of an amidoamine oxide type surfactant represented by the following general formula, and (b) / (a) Weight ratio is 1/100 to 100/100 and bulk density is 0.6 to 1.2g
/ Ml high density granular detergent composition. Embedded image (In the formula, R ₁ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₂ and R ₃ are H or an alkyl group or alkenyl group having 1 to 3 carbon atoms, and R ₄ is H or 1 to 5 carbon atoms. It is an alkyl group or an alkenyl group, and n is 1 to 5.) 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 5 to 30% by weight of the 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) (In the formula, M represents a group Ia element of the periodic table, and Me represents a group IIa. An element, a group IIb element, a group IIIa element, a group IVa element, or a group VIII element selected from one or more combinations,
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) (In the formula, M represents an alkali metal, x' = 1.5 to 2.6, y '
= 0 to 20. ) 4. The high-density granular detergent composition according to claim 1, which contains 1 to 30% by weight of an organic builder represented by the following formulas (1) to (2). Embedded image 5. The (a) anionic surfactant has 10 to 10 carbon atoms.
18 higher fatty acid salts, 1 straight or branched chain with 10 to 18 carbon atoms
Sulfate ester salt of secondary or secondary alcohol, carbon number 8 ~
Sulfate ester salt of ethoxylate of 20 alcohol, alkylbenzene sulfonate having 8 to 16 carbon atoms in alkyl group, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt and α-sulfo fatty acid alkyl The high-density granular detergent composition according to any one of claims 1 to 4, which is one kind or two or more kinds selected from ester salts. 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.