JPH09157696A - High density granular detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the washability of a high density granular detergent composition containing a specific ester type nonionic surfactant. SOLUTION: This high density granular detergent composition has a bulk density of 0.6-1.2g/ml and comprises 2-50wt.% of a nonionic surfactant of the formula [R1 is a 5-21C alkyl or alkenyl; R2 is a 2-4C alkylene; R3 is a 1-4C alkyl; (n) is 5-15], 3-50wt.% of an anionic surfactant, and 0.5-10wt.% of one or more kinds of a polyether compound, its fatty acid ester and its cationized. The polyether compound has a mol.wt. of 1,000-100,000 and is obtained by addition-reacting ethylene oxide and propylene oxide to a compound having five or more active hydrogen atoms so that the total weight of the parts of the polyoxyethylene chains is >=50wt.% based on the whole weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to high density granular detergent compositions having improved detergency. More specifically, it is a high density compound containing an ester type nonionic surfactant, an anionic surfactant, a compound containing ethylene oxide and propylene oxide added to a compound containing 5 or more active hydrogen atoms, and a derivative thereof, which has excellent detergency. Regarding granular detergent.

[0002]

2. Description of the Related Art A detergent for clothes solubilizes or emulsifies dirt,
A surfactant that disperses and dissolves and disperses from the fibers in the washing liquid, an alkaline agent that promotes decomposition and solubilization of soil, a polymer compound that disperses soil, and calcium and magnesium that reduce the ability of the surfactant. A metal ion sequestering agent and the like are basically mixed.

Of these components, the cleaning performance by itself is small, but by combining with a surfactant, etc.,
What improves the detergency is generally called a builder for detergents. As a builder for detergents, phosphorus compounds such as sodium tripolyphosphate, crystalline sodium aluminosilicate (zeolite) having a specific structure, crystalline silicate,
Citric acid, nitrilotriacetate, ethylenediaminetetraacetate, hydroxyiminodisuccinate, acrylic acid / maleic acid copolymer salt (eg, Socalan CP45, manufactured by BASF)
Polymer salts of vinyl compounds having a carboxyl group such as are often used. These capture calcium and magnesium ions in water, more effectively develop the performance of the surfactant, and impart an alkaline buffering capacity,
It has the effect of improving the dispersibility of inorganic solids such as mud and enhancing the cleaning ability.

JP-A-58-217598 describes the use of a nonionic surfactant represented by the following formula (I) in a detergent composition. In addition, JP-A-5-170714
Japanese Patent Laid-Open No. 5-202382 and Japanese Patent Laid-Open No. 5-202382 also describe use as a conventional detergent composition. As a high-density granular detergent composition, Japanese Patent Laid-Open No. 6-100887,
There are JP-A-6-166599, JP-A-6-192698 and others.

[0005]

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(Wherein R ₁ is an alkyl group or an alkenyl group having 5 to 21 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms,
R ₃ is an alkyl group having 1 to 4 carbon atoms, and n is 5 to 15.

[0007]

However, (I)
Regarding the detergent composition using the nonionic surfactant represented by the formula, it is considered that the detergency can be further improved, but a combined system with a builder that can achieve this object is still known. Absent. Under such circumstances, an object of the present invention is to find a builder capable of further improving the detergency in a system containing the surfactant represented by the formula (I), and to provide a high-density detergent having an excellent detergency. .

[0008]

Means for Solving the Problems As a result of various studies, the present inventors have found that a nonionic surfactant represented by the formula (I) is mixed with an anionic surfactant at a specific ratio to obtain a specific nonionic surfactant. It has been found that the detergency is further improved by adding an ionic builder in a specific ratio, and the present invention has been completed.

That is, the present invention provides (a) a nonionic surfactant represented by the following general formula (I):
2-50% by weight

[0010]

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(Wherein R ₁ is an alkyl or alkenyl group having 5 to 21 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R _{3 is}
Is an alkyl group having 1 to 4 carbon atoms, and n is a number of 5 to 15. ) (B) Anionic surfactant 3 to 50% by weight (c) In a compound having 5 or more active hydrogens, the total weight of ethylene oxide and propylene oxide in the polyoxyethylene chain portion is 50% or more of the total weight. Thus obtained and having an average molecular weight of 1,000 to 100,000, or one or a mixture of two or more fatty acid ester compounds or cation compounds thereof.
A high density granular detergent composition containing 10% by weight and having a bulk density of 0.6 to 1.2 g / ml. Hereinafter, the high-density granular detergent composition of the present invention will be described in detail.

<(A) Nonionic Surfactant> The ester type nonionic surfactant used in the present invention is a surfactant represented by the above general formula (I). Since this compound has an alkyl group having 1 to 4 carbon atoms as R _{3 at} the terminal, it has an effect of excellent detergency and good defoaming. In the present invention, the nonionic surfactant as the component (a) is blended in the composition in an amount of 2 to 50% by weight, preferably 5 to 30% by weight, from the viewpoints of detergency and defoaming property.

<(B) Anionic Surfactant> As the anionic surfactant as the component (b), a higher fatty acid salt having 10 to 18 carbon atoms, a linear or branched primary or branched chain having 10 to 18 carbon atoms or 2 Sulfate ester salts of primary alcohols, Sulfate ester salts of ethoxylates of alcohols having 8 to 20 carbon atoms, alkylbenzene sulfonates, paraffin sulfonates, α
One or more selected from -olefin sulfonate and α-sulfo fatty acid alkyl ester salt are preferable. The component (b), an anionic surfactant, is contained in the composition in an amount of 3 to 50% by weight, preferably 6 in terms of cleaning performance and defoaming property.
~ 35 wt% is compounded.

<(C) Nonionic Builder> The nonionic builder used in the present invention is a compound having 5 or more active hydrogens, and ethylene oxide and propylene oxide are the total weight of the polyoxyethylene chain portion. Of weight
It is a polyether compound having an average molecular weight of 1,000 to 100,000 or one or a mixture of two or more kinds of fatty acid esterified products or cationized products thereof, which is obtained by adding 50% or more. Particularly, the molecular weight of the polyether compound as the component (c) is preferably 5,000 to 50,000, and the total weight of the polyoxyethylene chain portion is 80 to 98% of the total weight.
%. The addition of ethylene oxide and propylene oxide may be block addition or random addition, but block addition is preferred. Under these conditions, the most suitable detergency can be obtained. Also,
Examples of the compound having 5 or more active hydrogens as the raw material of the component (c) include sorbitol, polyglycerin, alkylphenol formalin condensates (average condensation degree of 5 or more),
Triethylenetetramine, tetraethylenepentamine,
Examples include oleic acid amides of polyethyleneimine and tetraethylenepentamine. From the viewpoint of cleaning performance, the component (c) is 0.5 to 10% by weight, preferably 1 to 7% by weight in the composition.
% By weight. The nonionic surfactant as the component (a) is known and is disclosed in many patent publications as described above, but the use of the nonionic builder (c) of the present invention improves the detergency. Was not known at all.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The high-density granular detergent composition of the present invention comprises the following components other than the above-mentioned components (a), (b), and (c).
The components (d), (e), (f) and (g) are preferably blended in the following proportions.

<(D) Aluminosilicate> In general, aluminosilicate is represented by the following formula, and they can be used in the present invention. a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ w (H ₂ O) (where M is an alkali metal atom, a, b, and w represent the molar ratio of each component, and 0.7 <a ≤ 1.5, 0.8 <b
≤6, w is an arbitrary positive number. Among these, those represented by the following general formula are preferable. (Na ₂ O) · Al ₂ O ₃ · n (SiO ₂ ) · w (H ₂ O) (where n is 1.8 to 3.0 and w is a number of 1 to 6) As the aluminosilicate, A synthetic zeolite having an average primary particle size of 0.1 to 10 μm, represented by A type, X type and P type, is preferably used. Zeolite may be blended as zeolite agglomerated dry particles obtained by drying powder and / or zeolite slurry. In the present invention, the aluminosilicate (d) component is blended in the composition in an amount of 1 to 35% by weight, preferably 5 to 25% by weight, from the viewpoint of cleaning performance.

<(E) Crystalline silicate> As the crystalline silicate used in the present invention, those having the following composition are preferably exemplified. _{xM 2 O · ySiO 2 · zMe} m O n · wH 2 O (II) ( wherein, M is Group Ia elements of the periodic table, Me represents IIa, II
b, IIIa, IVa, or a combination of two or more selected from the group VIII elements, y / x = 0.5 to 2.6,
z / x = 0.01 to 1.0, n / m = 0.5 to 2.0, w = 0 to 20
It is. _{) 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 having the above composition will be described.
In the general formula (II), M is selected from the group Ia elements of the periodic table, and examples of the 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 form the M ₂ O component. Me is selected from the IIa, IIb, IIIa, IVa, or VIII group elements of the periodic table, and examples thereof include Mg, Ca, Zn, Y, Ti, Zr, and Fe. These are not particularly limited, but are preferably Mg and Ca from the viewpoint of resources and safety. Also,
These may be used alone or in combination of two or more,
For example MgO, may constitute the Me _m O _n component by mixing and CaO. Further, the crystalline silicate in the present invention may be a hydrate, and the hydration amount in this case is in the range of w = 0 to 20.

In the general formula, y / x is 0.5 to 2.6.
And preferably 1.5 to 2.2. If y / x is less than 0.5, the powder properties of the detergent composition such as caking property are adversely affected. When y / x exceeds 2.6, the detergency decreases. z / x is 0.01 to 1.0, preferably
It is between 0.02 and 0.9. If z / x is less than 0.01, the water resistance is insufficient, and if it exceeds 1.0, the ion exchange capacity tends to be low.
Insufficient as an ion exchanger. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. In addition, as described above, xM ₂
When O becomes x'Na ₂ O · x "K ₂ O, x becomes x '+ x". This relationship is the same in the z in the case of ZME _m O _n component composed of two or more. Further, n / m = 0.5 to 2.0 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 in the present invention comprises three components of M ₂ O, SiO ₂ and Me _m O _n as shown in the above general formula. Therefore, in order to produce the crystalline silicate in the present invention, 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, M
The e _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 and the like, as a material of Me _m O _n component, CaC
O ₃ , MgCO ₃ , Ca (OH) ₂ , Mg (OH) ₂ , MgO,
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 in the present invention is usually carried out by mixing the above-mentioned raw material components in a predetermined quantitative ratio so as to obtain the desired x, y, and z values of the crystalline silicate.
~ 1500C, preferably 500-1000C, more preferably
A method of firing at a temperature in the range of 600 to 900 ° C. for crystallization is exemplified. In this case, if the heating temperature is less than 300 ° C., crystallization is insufficient and water resistance is poor, and if it exceeds 1500 ° C., coarse particles are formed and the ion exchange ability is lowered. 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 in the present invention 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 a substance having an ion trapping ability in the present invention. one of.

In the present invention, the crystalline silicate preferably has an average particle size of 0.1 to 60 μm, more preferably 1 to 40 μm, still more preferably 10 to 30 μm. Within this range, a high ion exchange expression rate can be obtained. Further, if it is less than this range, the hygroscopicity and CO ₂ absorption are increased due to the increase of the specific surface area, and the quality tends to be deteriorated. The average particle size here is
It is the median diameter 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.

Next, the crystalline silicate having the above composition will be described. This crystalline silicate has 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. ), The general formula (I
In II), x ′ and y ′ are preferably 1.7 ≦ x ′ ≦ 2.2 and y ′ = 0, and the cation exchange capacity is 100 to 400 CaCO ₃ mg / g.
One of the substances having an ion-trapping ability in the present invention can be used.

Such a crystalline silicate is disclosed in JP-A-60-22.
No. 7895 describes the production method, and is generally obtained by firing amorphous glassy sodium silicate at 200 to 1000 ° C. to make it crystalline. Details of the synthesis method are described in, for example, Phys. Chem. Glasses. 7, 127-138 (1966), Z.
Kristallogr., 129 , 396-404 (1969). The crystalline silicate is available from Hoechst under the trade name “Na-SKS-6” (δ-Na ₂ Si ₂ O ₅ ) in powder or granular form. In the present invention, the crystalline silicate having a composition of, like the composition of, has an average particle size of preferably 0.1 to 60 μm, more preferably 1 to 40 μm, and further preferably 10 to 30 μm. .

In the present invention, the crystalline silicates having the above compositions and can be used alone or in combination of two or more kinds.

In the present invention, the crystalline silicate as the component (e) is used in the composition in an amount of 3 to 40 from the viewpoints of detergency and freedom of blending.
%, Preferably 5 to 30% by weight. Further, of the alkaline agents mixed in the composition, the component (e) is 50 to 10
It is desirable to occupy 0% by weight, preferably 70 to 100% by weight.

<(F) Inorganic other than the above components (d) and (e) or /
And organic builders> (1) Inorganic builders 1) Sodium carbonate, potassium carbonate, sodium bicarbonate,
Alkaline salts such as sodium sulfite and sodium sesquicarbonate. 2) Neutral salts such as sodium sulfate. 3) Orthophosphate, pyrophosphate, tripolyphosphate,
Phosphates such as metaphosphate, hexametaphosphate and phytate (alkali metal salts such as sodium and potassium).

(2) Organic builder The following substances are exemplified as the organic builder. 1) ethane-1,1-diphosphonic acid, ethane-1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane- 1,2-dicarboxy-1,2-diphosphonic acid, salts of phosphonic acids such as methanehydroxyphosphonic acid 2) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, Salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid 3) Salts of amino acids such as aspartic acid and glutamic acid 4) Aminopolyacetates such as nitrilotriacetate, ethylenediaminetetraacetate and diethylenediaminepentaacetate 5) Polyacrylic acid, polyglyoxylate salt described in JP-A-54-52196, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, Limethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, anhydrous Maleic acid-ethylene copolymer, maleic anhydride-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic acid ester copolymer, anhydrous Maleic acid-butadiene copolymer, maleic anhydride-isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid, ethylene copolymer, itaconic acid-aconic acid copolymer Combined, itaconic acid-maleic acid copolymer, itaconic acid-acetic acid Le acid copolymer, malonic acid - methylene copolymer, itaconic acid - fumaric acid copolymer,
Acrylic acid-maleic acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, Polyester polyaldehyde carboxylic acid having quaternary ammonium group, cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), starch succinic acid or maleic acid or terephthalic acid Ester, starch phosphate, dicarboxy starch, dicarboxymethyl starch, carboxymethyl cellulose, succinate,
Polyelectrolytes such as polyaspartic acid 6) Polyethylene glycol, polyvinyl alcohol,
Polyvinylpyrrolidone, carboxymethylcellulose,
Non-dissociated polymers such as cold water-soluble urethane-modified polyvinyl alcohol 7) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3, 4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, sucrose, lactose, carboxymethylated products such as raffinose, pentaerythritol carboxymethylated product, gluconic acid carboxylated product Methylated products, condensates of polyhydric alcohols or saccharides with maleic anhydride or succinic anhydride, condensates of oxycarboxylic acids with maleic anhydride or succinic anhydride, benzene polycarboxylic acids represented by melitic acid, ethane- 1,1,2,2-tetracarboxylic acid, ethene-1,
1,2,2-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, propane-1,2,3-tricarboxylic acid, butane-1,4-dicarboxylic acid, oxalic acid, sulfosuccinic acid,
Decane-1,10-dicarboxylic acid, sulfotricarballylic acid, sulhuitaconic acid, malic acid, oxydisuccinic acid,
Organic acid salts such as gluconic acid, CMOS, and Builder M.

Among these builders, especially the average molecular weight
The polyelectrolyte of 1,000 to 200,000 5) has excellent stain-dispersing performance, and it is preferable to add 1 to 20% by weight to the composition.

<(G) Others> The high-density granular detergent composition of the present invention further comprises a bleaching agent, a bleach activator, an enzyme, an enzyme stabilizer, a blue additive, an anti-caking agent, in addition to the above components.
Antioxidants, fluorescent dyes, fragrances, oil absorbing carriers, and other surfactants can be added.

(1) Bleaching agent As the bleaching agent, sodium percarbonate, sodium perborate (preferably monohydrate), sodium sulfate hydrogen peroxide adduct and the like can be mentioned, and sodium percarbonate is particularly preferable.

(2) Bleach Activator As the bleach activator, tetraacetylethylenediamine, acetoxybenzenesulfonate, JP-A-59-2299.
No. 9, JP-A-63-258447, JP-A-6-316700
Examples thereof include organic peracid precursors described in Japanese Patent Laid-Open Publication No. 2003-242242, and metal catalysts obtained by stabilizing a transition metal with a sequestering agent.

(3) Enzymes (which are enzymes that inherently perform the enzyme action during the washing step) Classifying from the reactivity of enzymes, hydrolases, hydrolases, oxidoreductases, desmolases, transferases and isomerases. However, any of them can be applied to the present invention. Particularly preferred are hydrolases, proteases, esterases,
Includes lipases, carbohydrases, nucleases, cellulases and amylases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin,
BPN, papain, promerin, carboxypeptidase A and B, aminopeptidase, and aspergillopeptidase A and B. As commercial products, sabinase, alcalase (Novo Industry Co., Ltd.), API 21 (Showa Denko)
Proc. K-14 or K- described in JP-A-5-43892.
There are 16. Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphotases. As the lipase, a commercially available lipase such as lipolase (Novo Industries) can be used. Specific examples of carbohydrases include cellulase,
Maltase, saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase. Further, as cellulase, commercially available cellzyme (Novo Industry Co., Ltd.), JP-A-63-2646
The cellulase described in claim 4 of Japanese Patent Publication No. 99 can be used, and as the amylase, commercially available Termamyl (Novo Industry Co., Ltd.) and the like can be used.

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

(5) Blue tinting agent Various blue tinting agents can be added as required. For example, the structures of the following formulas (i) and (ii) are recommended.

[0037]

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(Wherein 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. )

[0039]

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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. (6) Anti-caking agent Examples of anti-caking agents 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. (7) Antioxidant As the antioxidant, tertiary butyl hydroxytoluene,
4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis- (6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, mono Styrenated phenol, distyrenated phenol, 1,1′-bis- (4-hydroxyphenyl) cyclohexane and the like can be mentioned.

(8) Fluorescent dye As a fluorescent dye, 4,4'-bis- (2-sulfostyryl) is used.
-Biphenyl salt, 4,4'-bis- (4-chloro-3-sulfostyryl) -biphenyl salt, 2- (styrylphenyl) naphthothiazole derivative, 4,4'-bis (triazol-2-yl) stilbene derivative One or more bis (triazinylamino) stilbene disulfonic acid derivatives may be contained in the composition in an amount of 0 to 1% by weight. In particular, it is preferable to mix the biphenyl-type and stilbene-type fluorescent dyes at the same weight ratio. (9) Photoactivated bleaching agent One or two kinds of sulfonated aluminum phthalocyanine and sulfonated zinc phthalocyanine are contained in the composition in an amount of 0 to 0.2.
It may be contained in a weight percentage. (10) Fragrance As the fragrance, fragrances conventionally used in detergents, for example, fragrances described in JP-A-63-101496 can be used.

(11) Oil-absorptive carrier When increasing the amount of the component (a), it is preferable for stabilizing the physical properties of the powder, and a silica compound can be used. An oil absorption capacity of 100 ml / 100 g or more is suitable, and commercially available products include TIXOLEX 25 (Kofran Chemical Co., Ltd.), Tokusil AL-1 (Tokuyama Soda Co., Ltd.), Nipseal (Nippon Silica Co., Ltd.), etc. . As the oil-absorbing carrier, a part of the amorphous aluminosilicate of the component (d) can be used, but it is preferably JP-A-6-179899.
Those described in No. can be used.

Furthermore, the detergent composition of the present invention contains
A surfactant other than the components (a) and (b) can be blended. As the surfactant other than the components (a) and (b), a general nonionic surfactant, cationic surfactant or amphoteric surfactant may be used.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxypropylene alkyl ethers, polyoxypropylene alkenyl ethers, polyoxybutylene alkyl ethers, and polyoxybutylene. Alkenyl ethers, sucrose fatty acid esters, fatty acid glycerin monoesters, higher fatty acid alkanolamides, polyoxyethylene higher fatty acid alkanolamides, amine oxides and alkyl glycosides, preferably represented by the following general formula (A) Examples thereof include alkyl glycosides. R ³ (OR ⁴ ) _x G _y (A) (In the formula, R ³ is a linear or branched alkyl group having an average carbon number of 8 to 18, an alkenyl group or an alkylphenyl group, and R ⁴ is an average carbon number of 2 to 4 alkylene group, G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, x is an average number of 0 to 6, and y is an average number of 1 to 10.) In addition, a cationic surfactant is used. By blending it, it becomes possible to impart flexibility. A cationic surfactant may be added as long as this effect is not impaired, but it is usually 0.1 to 5
% By weight.

As other surfactants, for example, amphoteric surfactants such as alkylcarbobetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidohydroxysulfobetaine, alkylamidoamine type betaine and alkylimidazoline type betaine are effective. It can be blended as long as it does not inhibit.

The high-density detergent composition of the present invention is a powder or granular composition, but the production method is not particularly limited, and conventionally known methods can be used. In particular, spray-dried particles obtained by spray-drying an aqueous slurry of each component having a water content of 30 to 80% by weight, preferably 35 to 60% by weight, preferably granulating the spray-dried particles to increase the bulk density Is desirable. Alternatively, a method may be used in which an unneutralized product is directly neutralized and mixed with an alkali agent such as an alkali metal hydroxide, kneaded with other washing builders, and then cooled and pulverized after mixing. . High bulk density is disclosed in JP-A-61-69
897, JP 61-69899, JP 61-6990
No. 0, JP-A-2-222498, JP-A-2-222499
The methods described in JP-A-3-33199, JP-A-5-86400, and JP-A-5-209200 can be used. In addition, when a crystalline aluminosilicate is blended as the aluminosilicate of the component (d), it is used as a surface modifier of the granulated product. May be added to. Further, it is preferable that the crystalline silicate as the component (e) is not added to the slurry but is added at the time of granulating the spray-dried particles and increasing the bulk density.
When an alkali metal carbonate and / or an alkali metal silicate such as JIS No. 1 and No. 2 sodium silicate is added, it may be added to either the slurry or the granulation, and the alkali metal silicate is particularly a slurry. By adding in, it is possible to obtain spray-dried particles having excellent powder properties,
It is easy to handle in manufacturing.

The average particle size of the high-density granular detergent composition of the present invention is preferably 200 to 1000 μm, particularly 200 to 600 μm in order to obtain preferable powder properties. Further, the bulk density of the detergent composition of the present invention is 0.5 to 1.2 g / ml, preferably 0.1.
It is about 6 to 1.0 g / ml.

[0048]

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 The starting material of the nonionic organic builder of the component (c) used in the test in this example, the kind and the molar ratio of the alkylene oxide,
The molecular weights and symbols are shown in Table 1.

[0050]

[Table 1]

(Note) 1) PO: propylene oxide, EO: ethylene oxide 2) Weight ratio 3) Esterification ratio to terminal hydroxyl groups 4) Cationization ratio per nitrogen atom.

<Preparation of High Density Granular Detergent Composition> (1) The product 1 of the present invention in Table 2 was prepared by the following method. Nonionic surfactant [R ₁ = C ₁₁ H ₂₃ in the formula (I), n = 12, R ₂ = C ₂
H ₄ , R ₃ = CH ₃ ] 0.5 kg, LAS 3.0 kg, FA 0.4 kg, sample c-1 in Table 1 0.4 kg, fluorescent dye (4,4′-bis-
(2-sulfostyryl) -biphenyl salt) 0.05 kg, Table 1
C-7 component (0.4 kg) and soda ash (0.85 kg) to prepare a slurry having a water content of 50% by weight, and spray-drying the resulting slurry to obtain a high speed mixer (stirring granulator, Fukae Kogyo Co., Ltd.). 0.5 kg of zeolite and silicate (I
I) 2.0 kg was added for granulation, and 0.3 kg of zeolite was further added for granulation.
A high-density granular detergent composition was obtained by dry-mixing soda ash and 0.1 kg of enzyme (average particle size 410 μm, bulk density
0.760 g / ml). (2) Further, the composition using the porous silica compound,
According to the scheme of the system of the present invention product 21 shown below, both the present invention product and the comparative product were prepared with each mixing ratio. 1.0 kg of zeolite and 1.0 kg of soda ash were made into a water slurry of 60% solid content, and the particles obtained by spray-drying this were put into a Loedige mixer, and further 1.0 kg of porous silica compound, 2.0 kg of silicate, FA 0.4kg, enzyme 0.1kg, fluorescent dye 0.05k
g, soda ash were added, and while mixing and stirring these, a nonionic surfactant heated to 70 ° C. [in the formula (I)
R ₁ = C ₁₁ H ₂₃ , n = 12, R ₂ = C ₂ H ₄ , R ₃ = CH ₃ ] 2.0 kg was gradually added dropwise to obtain a high-density granular detergent composition (average particle size). Diameter 440 μm, bulk density 0.810 g / ml).

<Detergency test> The following detergency was evaluated using the various detergent compositions shown in Tables 2-7. The results are shown in Tables 2-7.

(Preparation of artificially contaminated cloth) 120 g of red edible earth for gardening
After drying at ± 5 ℃ for 4 hours, pulverize thoroughly and
After passing through a sieve (0 μm) for 2 hours at 120 ± 5 ° C, 150 g is dispersed in 1 liter of ethylene tetrachloride, and a cotton wire cloth 2023 is brought into contact with this solution and brushed to obtain a dispersion. Remove and remove excess adherent dirt to make a contaminated cloth.
This contaminated cloth was cut into 10 cm × 10 cm and used for the experiment. (Washing method) Terg-O-Tometer, 100r
pm), the above artificially contaminated cloth was used, and a cleaning test was performed under the following conditions using the product of the present invention and the comparative product, and the cleaning rate was calculated by the method described below. Bath ratio: 1/60 Water temperature: 25 ° C Washing time: 15 minutes Rinse: Tap water for 5 minutes Water hardness: 4 ° DH (calcium hard water) Detergent concentration: 0.0667% by weight (calculation of washing rate) Original cloth and washing The reflectance at 550 μm before and after was measured with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (D%) was calculated by the following formula. D = [(L ₂ −L ₁ ) / (L ₀ −L ₁ )] × 100 L ₀ : reflectance of original cloth L ₁ : reflectance of stained cloth before washing L ₂ : reflectance of stained cloth after washing

[0055]

[Table 2]

[0056]

[Table 3]

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[Table 6]

[0060]

[Table 7]

Nonionic surfactant: R _{1 in the} formula (I)
_{= C 11 H 23, n =} 12, R 3 = CH 3 · LAS: linear alkyl (C ₁ 2) benzenesulfonic acid Na
Salt ・ AS: dodecyl alcohol sulfate alcohol sulfate sodium salt ・ AES: polyoxyethylene (average addition mole number 2) dodecyl ether sulfate sodium salt ・ SAS: paraffin sulfonate sodium salt ・ FA: tallow fatty acid sodium salt ・ porosity Silica compound: Thixolex 25 (manufactured by Kofran Chemical Co., Ltd.)-Zeolite (crystalline aluminosilicate): Composition Na ₂ O ・ Al ₂ O ₃・ 3SiO ₂・ 2H ₂ O (average particle diameter 2 μm)
, Ion exchange capacity 290 CaCO ₃ mg / g) ・ Silicate (II): composition M ₂ O ・ 1.8SiO ₂・ 0.02 M'O (where M = Na, K
, K / Na = 0.03, M ′ = Ca, Mg, Mg / Ca = 0.01, ion exchange capacity 305 CaCO ₃ mg / g, average particle size 30 μm) ・ Silicate (III): composition Na ₂ O ・ 2SiO ₂ ( Ion exchange capacity 224 CaCO ₃ mg /
g, average particle diameter 30 μm) -Na salt of AA-MA copolymer: average molecular weight 70,000, acrylic acid (AA) / maleic acid (MA) = 7/3 (molar ratio) -builders other than the above: * 1: 3 -Hydroxy-2,2'-iminodisuccinic acid * 2: Na polyacrylate (average molecular weight 8000) -Na polyacrylate: Average molecular weight 8000-Common components: enzyme [sabinase 12.0TW, cellzyme 0.
7T, Termamill 6.0T (Equivalent mixture of Novo Industry) 0.9% and fluorescent dye [Chinopearl CBS-X
(Manufactured by Ciba Geigy): Whitetex SA (manufactured by Sumitomo Chemical Co., Ltd.) = 1: 1 (weight ratio) mixture] 0.6%
(Each in the composition) and a balanced amount of soda ash to bring the composition to 100. * 1: Comparative products 9 and 10 used polyoxyethylene (12 mol) dodecyl ether instead of component (a).

[0062]

EFFECTS OF THE INVENTION According to the present invention, a high-density granular detergent composition having more improved detergency can be obtained in a system containing a specific ester type nonionic surfactant.

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Claims (5)

[Claims] (A) 2 to 50% by weight of a nonionic surfactant represented by the following general formula (I): (In the formula, R ₁ is an alkyl group or an alkenyl group having 5 to 21 carbon atoms, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R ₃ is 1 to 1 carbon atoms.
4 is an alkyl group, and n is a number of 5 to 15. ) (B) Anionic surfactant 3 to 50% by weight (c) In a compound having 5 or more active hydrogens, the total weight of ethylene oxide and propylene oxide in the polyoxyethylene chain portion is 50% or more of the total weight. Thus obtained and having an average molecular weight of 1,000 to 100,000, or one or a mixture of two or more fatty acid ester compounds or cation compounds thereof.
A high density granular detergent composition containing 10% by weight and having a bulk density of 0.6 to 1.2 g / ml. 2. The high-density granular detergent composition according to claim 1, wherein the compounding amount of the component (c) is 1 to 7% by weight. 3. The anionic surfactant as the component (b) is an alkali metal salt of a higher fatty acid having 10 to 18 carbon atoms, or a straight-chain or branched chain primary or secondary alcohol sulfate ester alkali having 10 to 18 carbon atoms. Metal salts, sulfuric acid ester alkali metal salts of ethoxylates of alcohols having 8 to 20 carbon atoms,
The high-density granular detergent composition according to claim 1 or 2, which is one or more selected from alkali metal salts of alkylbenzene sulfonic acid, alkali metal salts of paraffin sulfonic acid, and alkali metal salts of α-sulfofatty acid alkyl ester. 4. The compound having 5 or more active hydrogens as the component (c) is sorbitol, an alkylphenol formalin condensate having an average degree of condensation of 5 or more, triethylenetetramine,
The high density granular detergent composition according to any one of claims 1 to 3, which is an oleic acid amide of tetraethylenepentamine, polyethyleneimine, or tetraethylenepentamine. 5. The molecular weight of component (c) is 5,000 to 50,000,
The total weight of the polyoxyethylene chain portion is 80% of the total weight.
It is -98%, The high-density granular detergent composition in any one of Claims 1-4.