JP3347180B2 - Powder detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery or granular detergent composition containing a nonionic surfactant as a main base detergent, and more particularly, to an improved elution rate of a nonionic surfactant from detergent particles. Powder detergent composition.

[0002]

2. Description of the Related Art Nonionic surfactants are characterized by good hard water resistance, outstanding detergency and dispersing power, and very good biodegradability. And is regarded as important as a surfactant for cleaning.

However, nonionic surfactants used for cleaning are usually liquid at room temperature, and
When blended in a large amount in a liquid detergent in a liquid state, the nonionic surfactant gradually exudes over time and penetrates into the inner surface of the paper container, or the fluidity of the powder detergent is significantly impaired. There is a problem that caking is caused and the detergent is hardened, thereby significantly impairing the commercial value.

[0004] It is known that silica-based materials can be used to improve the flowability of powder detergents containing non-ionic surfactants. For example, JP-A-50-19813 discloses a premix in which a nonionic surfactant is finely distributed on a zeolite or a mixture of a zeolite and an inorganic peroxide that generates hydrogen peroxide in water (in the premix). A fluid dispersant containing 30 to 100% and a spray-dried detergent of 0 to 70% is disclosed. JP-A-61-89300 discloses that after mixing a water-soluble powder and silica powder, a nonionic surfactant is sprayed,
Next, the granulated material is adjusted by adding zeolite powder, and the nonionic surfactant-containing granular detergent containing the granulated material and the granular detergent containing the anionic surfactant has good fluidity and can prevent caking. It has been disclosed.

JP-A-51-41708 discloses a free-flowing detergent composition containing a porous aggregate of a synthetic amorphous silica derivative and a nonionic surfactant.

However, when a silica-based substance is blended with a zeolite-containing detergent, the solubility tends to deteriorate with time under humidifying conditions, and further improvement is required.

To cope with such a problem, Japanese Patent Application Laid-Open No. 5-5100 discloses that the pH of a dispersion is 9 or more or a 2% aqueous NaOH solution.
By using an oil-absorbing carrier having a dissolution amount of 0.5 g or less per 100 ml, improvement in solubility over time and generation of water-insoluble substances are improved. As described above, a technique of inserting a nonionic surfactant into an oil-absorbing carrier and blending it into a powder detergent composition has been conventionally known, but studies on the basic dissolution behavior of detergent particles are insufficient. . In particular,
The nonionic surfactant impregnated in the oil-absorbing carrier elutes very slowly from the oil-absorbing carrier.
There is a problem that 0% is not eluted.

[0008]

Under such circumstances, the present inventors have conducted intensive studies on a powdery or granular detergent composition in which a nonionic surfactant is occluded in an oil-absorbing carrier. The present inventors have found that the incorporation of a derivative can improve the rate of dissolution of a nonionic surfactant from an oil-absorbing carrier in washing water, and completed the present invention.

That is, the present invention provides the following components (a), (b) and
It is intended to provide a powdery or granular cleaning composition containing a nonionic surfactant containing (c) as a main cleaning base. (a) One or more nonionic surfactants represented by the following general formulas (1) to (6) having a melting point of 40 ° C. or less: 10 to 40% by weight ・ Formula (1) R -(OR ') _n- OH [wherein, R represents a linear or branched alkyl group having 8 to 20 carbon atoms R'; an alkylene group n having 2 to 4 carbon atoms; and an average value of 3 to 20]. Formula (2) R ″ —CO (OR ′) _n -OR ′ ″ [wherein R ′: an alkylene group R ″ having 2 to 4 carbon atoms; linear or branched having 7 to 19 carbon atoms] Chain alkyl group R ′ ″; hydrogen or alkyl group having 2 to 3 carbon atoms n; average value is 3-20. Formula (3) R- (OR ′) _m -G _p [wherein, R is a linear or branched alkyl group R ′ having 8 to 20 carbon atoms; an alkylene group G having 2 to 4 carbon atoms; Residue m derived from reducing sugar of Formula 5 or 6; average value is 0-5 p; average value is 1-10. ]

[0010]

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(B) 5 to 60% by weight of an oil-absorbing carrier containing 30% by weight or more of silicon as SiO _{2 in} terms of anhydrous content and having an oil-absorbing capacity of 80 ml / 100 g or more. (C) The following general formula (I) It contains the indicated glycerin or its derivative in a weight ratio of (a) / (c) = 20/1 to 3/1.

[0012]

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As the nonionic surfactant (a) used in the present invention, at least one of the following nonionic surfactants represented by the following general formulas (1) to (6) is used. These nonionic surfactants have a melting point of 40 ° C. or lower, that is, a liquid or slurry at a temperature of 40 ° C. or lower. -Formula (1) R- (OR ') _n- OH [wherein, R; a linear or branched alkyl group R' having 8 to 20 carbon atoms R '; an alkylene group n having 2 to 4 carbon atoms; 3-20. Formula (2) R ″ —CO (OR ′) _n -OR ′ ″ [wherein R ′: an alkylene group R ″ having 2 to 4 carbon atoms; linear or branched having 7 to 19 carbon atoms] Chain alkyl group R ′ ″; hydrogen or alkyl group having 2 to 3 carbon atoms n; average value is 3-20. Formula (3) R- (OR ′) _m -G _p [wherein, R is a linear or branched alkyl group R ′ having 8 to 20 carbon atoms; an alkylene group G having 2 to 4 carbon atoms; Residue m derived from reducing sugar of Formula 5 or 6; average value is 0-5 p; average value is 1-10. ]

[0014]

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In particular, the main nonionic surfactants include:
Those represented by the formula (1) are preferable, and among them, those having 8 to 2 carbon atoms
0, preferably 10 to 15, particularly preferably 12 to 14, linear or branched chain, the average number of moles of ethylene oxide added to the primary or secondary alcohol is 3 to 15, preferably 5 to 12, more preferably 6 to 12. It is desirable to use ten polyoxyethylene alkyl ethers. Further, the polyoxyethylene alkyl ether generally contains a large amount of alkyl ether having a low addition mole number of ethylene oxide,
It is desirable to use one having a 3 mol adduct of 35% by weight or less, preferably 25% by weight or less. (a) The component is 10 to 40% by weight, preferably 15 to 30% by weight in the total composition.
Be blended.

The oil-absorbing carrier, which is the component (b) of the present invention, contains 30% by weight or more, preferably 40% by weight of silicon as SiO _{2 in} terms of anhydrous.
A silica-based oil-absorbing carrier containing at least 80% by weight, more preferably at least 70% by weight, and having an oil absorption capacity of at least 80 ml / 100 g, preferably at least 150 ml / 100 g. In addition, “containing 30% by weight or more of silicon as SiO _{2 on an} anhydrous basis” means that the oil-absorbing carrier in an anhydrous state from which water or bound water has been removed by drying or the like contains at least 30% by weight of silicon as SiO _2. means. Unless the oil absorption capacity is 80 ml / 100 g or more, the nonionic surfactant cannot be sufficiently absorbed. In the present invention, among such oil-absorbing carriers, amorphous ones are preferred because granulation is easy in production, and the pH of a 5% dispersion is preferably 9 or more (test method).
JIS K 6220) amorphous silica, amorphous aluminosilicate and the like are preferred in that they do not decrease the solubility after storage. Such an oil-absorbing carrier has an average particle size of 200 μm
Amorphous silica and amorphous aluminosilicate to a certain extent are commercially available, and in the present invention, a carrier may be selected from these. Examples of such oil-absorbing amorphous silica include Toksil AL-1 (Tokuyama Soda Co., Ltd.) and Nipsil
NA (Nippon Silica Co., Ltd.), Carplex # 100 (Shinogi Pharmaceutical Co., Ltd.), SIPERNATD10 (Degussa) and the like. Oil-absorbing carriers marketed under the trade name may be mentioned.

The oil-absorbing carrier exemplified above has almost no cation exchange ability. An oil-absorbing carrier having a cation exchange ability is advantageous because it also functions as a detergent builder.
An oil-absorbing amorphous aluminosilicate represented by the following general formula (1) is exemplified as an oil-absorbing carrier having high oil absorption and high cation exchange ability. a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (1) (In the formula, M represents an alkali metal atom, and a, b, and c represent the number of moles of each component. , 0.7 ≦ a ≦ 2.0, 0.8 ≦ b <4, c are arbitrary positive numbers. ] In particular the following general formula _{(2) Na 2 O · Al} 2 O 3 · m (SiO 2) · c (H 2 O) (2) [wherein, m is 1.8 to 3.2, c is a number from 1 to 6 Represents ]
Is preferably represented by The amorphous aluminosilicate having high oil absorbency and high ion exchange capacity which can be used in the present invention, the molar ratio of SiO ₂ and M ₂ O (M denotes an alkali metal) SiO ₂ / M ₂ O = is 1.0 to 4.0, the molar ratio of between H ₂ O and M ₂ O is in alkali metal silicate solution is a _{H 2 O / M 2 O =} 12~200, the molar ratio of M ₂ O and Al ₂ O ₃ is M ₂ O / Al ₂ O ₃ = 1.0 to 2.0
And the molar ratio of between H ₂ O and M ₂ O is _{H 2 O / M 2 O =} 6.0~500
15 low alkali alkali aluminate aqueous solution
Add under vigorous stirring at a temperature of 6060 ° 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 is then brought to 70-100 ° C, preferably 90-1 ° C.
It can be advantageously obtained by performing a heat treatment at a temperature of 00 ° C. for 10 minutes or more and 10 hours or less, preferably 5 hours or less, followed by filtration, washing and drying. Ion exchange capacity by this method
An amorphous aluminosilicate oil-absorbing carrier having a CaCaCO content of ₃ mg / g or more and an oil absorption capacity of 200 ml / 100 g or more can be easily obtained (see JP-A-62-191417 and JP-A-62-191419). ).

The pH of the 5% dispersion of the oil-absorbing carrier is JIS K 6220
Is measured based on That is, about 5 g of a sample is weighed and placed in a hard Erlenmeyer flask, 100 ml of water not containing carbonic acid is added, stoppered and shaken for 5 minutes. Using the solution after shaking as a test solution, the pH is measured by a glass electrode method (JIS Z8802 7.2.3). By selecting an oil-absorbing carrier having a pH of the 5% dispersion of 9.0 or more, a zeolite-containing nonionic powder detergent composition which does not deteriorate in solubility during storage can be obtained. When the pH of the 5% dispersion is less than 9.0, silicon
O ₂ as 30 wt% or more, oil-absorbing carrier containing in particular 70 wt% or more, significantly lowers the solubility of the detergent when it is stored under conditions of high temperature and high humidity.

Further, when the alkalinity of the detergent is very high or the storage condition is very severe, 2% Na is more severe.
It is preferable to select an oil-absorbing carrier that satisfies the condition that the amount dissolved in 100 ml of an OH aqueous solution is 0.5 g or less. That is, 10 g of the oil-absorbing carrier was dispersed in 100 ml of a 2% aqueous NaOH solution, and the mixture was stirred at 25 ° C. for 16 hours, and colorimetrically determined for SiO ₂ in the filtrate (colorimetric quantitative analysis was performed in Oil Chemistry, Vol. 25, p156, 1976). ) In which the amount of the oil-absorbing carrier is 0.5 g or less as the oil-absorbing carrier. An oil-absorbing carrier satisfying this condition can be found in the amorphous aluminosilicate represented by the general formula (2). On the other hand, some oil absorbing carriers
Even if the pH of the 5% dispersion is less than 9.0, a 2% aqueous NaOH solution 1
Although the amount dissolved in 00 ml is 0.5 g or less,
Such an oil-absorbing carrier is also included in the scope of the present invention.

In the present invention, an oil-absorbing carrier other than the conventionally known component (b) may be added to such an extent that the effects of the present invention are not impaired.

The oil-absorbing carrier of the component (b) is contained in the total composition in an amount of 5%.
-30% by weight, preferably 5-20% by weight.

The component (c) of the present invention is glycerin represented by the following general formula (I) or a derivative thereof.

[0023]

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In the general formula (I), the total average addition mole number (p + q + r) of the alkylene oxide is from 0 to 20, but if it exceeds 20, the effect of improving the solubility becomes insufficient. In the present invention, particularly, p + q + r in the general formula (I) is 10
Preferably the following, in particular R is -CH ₂ -CH ₂ - are preferred ones. The glycerin or the derivative thereof as the component (c) is blended in the total composition so that (a) / (c) = 20/1 to 3/1 (weight ratio), preferably 10/1 to 4/1. The amount in the composition is 0.5 to 10% by weight. (a) / (c) weight ratio is 2
If it exceeds 0/1, no solubility improving effect is exhibited, and 3
Even if it is less than / 1, there is no great difference in the dissolution rate, which is not preferable in terms of lowering the degree of freedom of blending.

The composition of the present invention may further have a molecular weight of 4,000 to 20,000.
By blending the polyethylene glycol of 1 to 5% by weight, preferably 1 to 3% by weight, powder properties during long-term storage are further improved.

The powder detergent composition of the present invention may contain, in addition to the above components, inorganic builders, organic builders, anti-redeposition agents, fluorescent dyes, enzymes, fragrances, and the like, which are usually added to detergents. The components (I) to (VII) that can be blended are exemplified below.

(I) Inorganic builder 1) Sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfite, sodium sesquicarbonate, JIS 1
Alkali metal silicates such as sodium silicate. However, the amount of the alkali metal silicate is desirably 5% by weight or less, preferably 1% by weight or less in the whole composition, in that the solubility is not lowered. 2) Neutral salts such as sodium sulfate. 3) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, metaphosphate, hexametaphosphate and phytate (alkali metal salts such as sodium and potassium). 4) Further, the following crystalline aluminosilicates or crystalline layered silicates different from the above alkali metal silicates can also be mentioned. Specific examples include a crystalline aluminosilicate represented by the following formula. x '(M ₂ O) .Al ₂ O ₃ .y' (SiO ₂ ) .w '(H ₂ O) (where M is an alkali metal atom such as sodium or potassium, x', y ', w' Represents the number of moles of each component, and generally,
0.7 ≦ x ′ ≦ 1.5, 0.8 ≦ y ′ ≦ 6, w ′ are arbitrary constants. Among them, those represented by the following general formula are particularly preferred. _{Na 2 O · Al 2 O 3} · ySiO 2 · wH 2 O ( wherein, y is 1.8 to 3.0, w is a number of 1-6.)
Further, the following formula M ₂ Si _x O _{(2x + 1)} · y (H ₂ O) (where M represents an alkali metal, and x and y are 1.5 ≦ x
≦ 4, y ≦ 25, preferably y ≦ 20. The crystalline layered silicate represented by the formula (1) is also included. This compound is disclosed in
The production method is described in JP-A-60-227895, which 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 layered silicate can be obtained in fine powder, powder, or granule form, for example, from Hoechst under the trade name “Na-SKS-6” (σ-Na ₂ Si ₂ O ₅ ). Can be used with a particle size of 10 to 500 μm, preferably 10 to 500 μm.
It is 300 μm.

Among these inorganic builders, sodium tripolyphosphate, sodium carbonate, crystalline aluminosilicate, and crystalline layered silicate are more preferred. In particular, as the crystalline aluminosilicate (zeolite), the average primary average particle diameter represented by A-type and X-type zeolites 0.1 to 10 μm
Is preferably used. The zeolite is blended as zeolite agglomerated dry particles obtained by drying the powder and / or the zeolite slurry. The zeolite may usually be blended in the total composition in an amount of 5 to 60% by weight.

(II) 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 derivatives thereof, 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, diethylenediaminepentaacetate 5) Polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, Livinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methylvinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride Acid-ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride Acid-isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid, ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer , Itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer, Phosphate - fumaric acid copolymer,
Ethylene glycol-ethylene terephthalate copolymer, vinyl pyrrolidone-vinyl acetate copolymer, 1-butene-2,3,4-tricarboxylic acid-itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid having a quaternary ammonium group Acid, cis-isomer of epoxysuccinic acid, poly [N, N-bis (carboxymethyl) acrylamide], poly (oxycarboxylic acid), densuccinic acid or maleic acid or terephthalic acid ester,
Polymer electrolytes such as starch phosphate, dicarboxystarch, dicarboxymethyl starch, carboxymethylcellulose, succinate, etc.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 organic builders, citrate, polyacrylate and polyethylene glycol are more preferred. Particularly preferred are trisodium citrate,
It is sodium polyacrylate.

(III) Enzymes As enzymes, conventionally known proteases, lipases, cellulases, amylases and the like may be blended.

(IV) Bleaching agents Examples of the bleaching agent include perborates and percarbonates.

(V) Bleaching activator As the bleaching activator, tetraacetylethylenediamine and organic compounds described in JP-A-59-22999, JP-A-63-258447 and JP-A-63-31566 can be used. Peracid precursors can be used.

(VI) Antifoaming agent As an antifoaming agent, a silicone derivative can be blended.
Granulated by the method described in JP-A-6307 can be used.

(VII) Others Other general fragrances blended in the detergent composition,
An optional component such as a fluorescent dye may be blended.

In the powder detergent composition of the present invention, a liquid nonionic surfactant is gradually added while mixing powder components such as an oil-absorbing carrier, carbonate and zeolite to obtain a uniform mixture. The method of adding glycerin or a derivative thereof is not particularly limited, and may be used by mixing with a liquid nonionic surfactant in advance. The granulation method is not particularly limited.
The method described in 3824 can be used. Also,
Powder such as crystalline aluminosilicate may be added as a generally known surface modifier to coat the surface of the granulated product. The average particle size of the powder detergent composition is 200-1000 μm
, Preferably from 300 to 700 in terms of physical properties of the powder during long-term storage. This average particle size is JIS Z 8801
Is measured from the weight fraction based on the size of the sieve after shaking for 5 minutes using a standard sieve.

In the present invention, an enzyme, a perborate,
When a percarbonate or a bleach activator is blended, it is preferable to perform after-blending on the granulated material containing the above-mentioned nonionic surfactant as a main component, and these may be granulated in advance.

The optional builder is preferably used as spray-dried particles. The spray-dried particles of the builder are obtained by drying an aqueous slurry of an organic or inorganic builder by a known spray-drying method. The water content of the aqueous slurry is preferably 30 to 80% by weight, more preferably 35 to 60% by weight. In the production of the builder spray-dried particles, one or more anionic, cationic or nonionic surfactants may be added, if necessary, to the builder spray-dried particles in an amount of 40% by weight or less, and other additives. You may add below 5 weight%. The average particle diameter of the builder spray-dried particles is preferably from 100 to 600 μm, more preferably
It is 150-400 μm.

The nonionic powder detergent composition of the present invention thus obtained is about 0.6 to 1.0 g / ml, preferably
It has a bulk density of 0.7-0.9 g / ml.

The present invention relates to a powder detergent composition in which a liquid nonionic surfactant as a main cleaning base is occluded in an oil-absorbing carrier, and the rate of elution of the nonionic surfactant from the oil-absorbing carrier is high. However, when an anionic surfactant is used in combination, the anionic surfactant is preferably contained in the entire composition.
When it is contained in an amount of not less than% by weight, the re-contamination-preventing property tends to decrease, and it is preferable to blend the composition under the following conditions. That is, a powdered or granular cleaning composition containing a nonionic surfactant as a main cleaning base (A) and a powdery or granular cleaning composition containing an anionic surfactant as a main cleaning base (B) And a weight ratio of (A) / (B) = 1/99 to 1
/ 1, preferably 1/20 to 4/5. If the (A) / (B) weight ratio is less than 1, the caking resistance tends to decrease. Further, the above-mentioned anionic surfactant as the main cleaning base powder or granular cleaning composition (B)
Preferably contains the following components (d), (e) and (f): (d) Sulfonate type anionic surfactant and / or sulfate ester type anionic surfactant 15 to 45% by weight (e) Crystalline synthetic aluminosilicate, crystalline layered silicate and citric acid or One or more divalent metal chelating agents selected from the group consisting of salts thereof 10 to 50% by weight (f) Alkali metal carbonate and / or alkali metal silicate 5 to 40% by weight The above-mentioned anionic surfactant The anionic surfactant of the component (d) of the powdery or granular detergent composition (B) whose main cleaning base is a sulfonate type anionic surfactant and / or a sulfate ester type anion Surfactants, specifically, alkyl benzene sulfonate having 8 to 22 carbon atoms, alkyl or alkenyl polyoxyethylene and / or polyoxypropylene sulfate, alkyl or alkenyl sulfate, α-sulfofatty acid Ester salts of salt or α- sulfofatty acids, alkanesulfonic acid salts, and the like. Among them, alkali metal salts of alkylbenzenesulfonic acid, alkylpolyoxyethylene sulfate and alkyl sulfate having 10 to 16 carbon atoms are preferable. The anionic surfactant (d) is incorporated in the detergent composition (B) in an amount of 15 to 45% by weight, preferably 20 to 30% by weight.

The components (e) and (f) used in the powder or granular detergent composition (B) containing an anionic surfactant as a main cleaning base are mainly composed of the above-mentioned nonionic surfactant. The same powdery or granular detergent composition (A) as the base is used. The component (e) is incorporated in the detergent composition (B) in an amount of 10 to 50% by weight, preferably 20 to 40% by weight,
The component (f) is incorporated in the detergent composition (B) in an amount of 5 to 40% by weight, preferably 10 to 30% by weight.

The detergent composition (B) has a composition in which an anionic surfactant is used as a main detergent, but has a carbon number of an alkyl chain.
12-18 and the average number of moles of ethylene oxide added is 5
A small amount of up to 20 nonionic surfactants can be blended, and the blending amount in the composition is preferably 5% by weight or less.

The detergent composition (B) has a water content of 30 to
It is desirable to use spray-dried particles obtained by spray-drying an aqueous slurry of 80% by weight, preferably 35 to 60% by weight, and preferably those obtained by granulating the spray-dried particles to have a high bulk density. To increase the bulk density, JP-A-61-69897,
The methods described in JP-A-61-69899 and JP-A-61-69900 can be used. Of the component (e) related to the detergent composition (B), a small amount of crystalline aluminosilicate is used during or after granulation in addition to the slurry to be used as a surface modifier for the granulated material. It may be added immediately before. Also,
Among the components (e), it is preferable that the crystalline layered silicate is not added to the slurry but is added at the time of granulation and high bulk density of the spray-dried particles. The component (f) may be added to either the slurry or the granulation.Particularly, by adding the alkali metal silicate to the slurry, spray-dried particles having excellent powder physical properties can be obtained, and The above handling becomes easy. It can also be used as a binder during granulation.

The average particle size of the powder or granular detergent composition (B) containing an anionic surfactant as a main washing base is 200 to 1000 μm, preferably 200 to 600 μm, in order to obtain preferable powder properties.
μm is desirable. When the average particle diameter of the detergent composition (B) is less than 200 μm, caking becomes easy.

Other components that can be blended into the detergent composition (B) include the above-mentioned optional components (I) to (VII). The optional components to be added to the detergent compositions (A) and (B) should be added to either the detergent composition (A) or (B) in consideration of the handling during manufacture and the properties of the components. May be used or, if there is no problem, they may be blended in both.

It is preferable that the detergent compositions (A) and (B) are separately granulated and then dry-mixed. As described above, release of hydrogen peroxide such as sodium percarbonate and sodium perborate is performed. The body or an organic peracid precursor such as tetraacetylethylenediamine, an enzyme, an antifoaming agent, a fragrance, and the like may be separately blended and after-blended. Detergent composition (A) and
The bulk density of the powder detergent composition obtained by mixing (B) and optional components to be added as required is 0.5 to 1.0 g / cm ³ , preferably 0.6 to 0.9 g / cm ³ .

[0047]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example Sodium carbonate was dissolved in ion-exchanged water to prepare a 6% aqueous solution. 132 g of this aqueous solution and 38.28 g of a 50% aqueous sodium aluminate solution were placed in a 1000 cc reaction tank equipped with baffles. No. 3 water glass 201.4 diluted with 2 times water in this solution
g was dropped for 20 minutes under strong stirring at 40 ° C., CO ₂ gas was blown in to control the pH of the reaction system (pH = 10.5),
The reaction rate was optimized. After the reaction, the mixture was heated to 50 ° C. and aged for 30 minutes. Thereafter, CO ₂ gas was blown into the mixture to neutralize excess alkali (pH = 9.0). This neutralized slurry was filtered under reduced pressure using filter paper (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.). The filter cake is washed with water 1000 times and filtered and dried (105 ° C, 30 ° C).
0 torr, 10 hours). After further crushing, an amorphous aluminosilicate powder was obtained. As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained powder was as follows: Al ₂ O ₃ = 29.6% by weight, Si
O ₂ = 52.4% by weight and Na ₂ O = 18.0% by weight (1.0Na ₂ O
・ Al ₂ O ₃・ 3.01SiO ₂ ). In addition, the ability to capture Ca ions is 165 CaC
O ₃ mg / g, oil absorption capacity was 265 ml / 100 g. Also, 5
The pH of the% dispersion was 10.2, and the dissolution amount in a 2% aqueous NaOH solution was 0.10 g.

Example 1 Various oil-absorbing carriers having the properties shown in Table 1 (the pH of the 5% dispersion in Table 1 is a value measured based on JIS K 6220), Amount of crystalline aluminosilicate shown in Table 2 or Table 3, 3% by weight of tallow soap, average molecular weight 50
3% by weight of sodium polyacrylate, 0.5% by weight of fluorescent dye, 20% by weight of zeolite 4A, and a balanced amount of sodium carbonate in a batch kneader (Ile Shokai Bench Kneader PNV
-1), gradually introduce a mixture of a liquid nonionic surfactant and glycerin or a derivative thereof, then add 2% by weight of a polyethylene glycol melt having an average molecular weight of 12000, and sieve the particles having a particle diameter of 1000 μm or more. Particles and 125
A powder detergent fabric having an average particle diameter of 380 to 400 μm was obtained except for particles having a particle diameter of μm or less. 0.5% by weight of enzyme and 0.3% of fragrance
5% by weight of zeolite 4A was added and mixed to obtain a final detergent product. For this detergent product, the measurement of the dissolution rate of the nonionic surfactant in water and the solubility test of detergent particles over time under humidified conditions were carried out by the following methods. Table 2 or Table 3 shows the results.

[Evaluation Method] Measurement of Dissolution Rate (Dissolution Rate) of Nonionic Surfactant 3 L of tap water at 20 ° C. is put into a beaker. After allowing this to stand, 2.5 g of the powder detergent composition is added and stirred with a magnetic stirrer. After 5 minutes of stirring, sample 10 ml and immediately filter. The amount of the nonionic surfactant in the filtrate is quantified by the cobalt thiocyanate method, and the elution rate of the nonionic surfactant is determined from the following equation. The cobalt thiocyanate method was carried out according to the method described on page 324 of "Surfactant Analysis Method" (edited by Surfactant Analysis Research Group, published by Koshobo, 1987).

[0051]

(Equation 1)

2. Dissolution test with time Put the detergent in a Petri dish, leave it at 30 ° C and 70% RH for 1 day, sample 0.83g, add it to 10 ° C and 1 liter of tap water, stir with a magnetic stirrer for 10 minutes,
The mixture is filtered through a 00 mesh wire net, and the filtration residual ratio (%) after drying is determined.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

Example 2 (1) Production of Detergent Composition Among the components shown in Table 4, a slurry (water content: 40% by weight) of components forming spray-dried particles was prepared and spray-dried. The powder is put into a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), and the after-blended components are dry-mixed to obtain an average particle diameter of 400 to 430 μm and bulk density.
A high-density granular detergent composition (B) containing 0.70 to 0.80 g / cm ^{3 of} an anionic surfactant as a main cleaning base was obtained (products (a) to (d) of the present invention in Table 4). Next, these granular detergent compositions (B) were used in Table 1 of Example 1 and the product No. 10 of the present invention [non-ionic surfactant was used as the main cleaning base powder cleaning composition (A)] and Table 5 And the desired final detergent product was obtained. With respect to these detergent products, the re-staining effect and the elution rate (elution rate) of the nonionic surfactant were measured by the following methods. Table 5 shows the results.

[Evaluation Method] Anti-recontamination property Dissolve detergent in 4 ° DH hard water, and add 0.0833 wt% detergent aqueous solution 1
Make up a liter. Add 0.2 g of carbon black to this, stir well and disperse, and use a tergotometer ("mode
l 400 ", Ueshima Seisakusho) stainless steel beaker
After washing with 5 pieces of 10 × 10 cm cotton / polyester = 65/35 (weight ratio) blended cloth at 100 rpm and 20 ° C. for 15 minutes, the cloth is dehydrated, and similarly rinsed with 4 ° DH hard water for 5 minutes for 2 minutes. Repeat several times. After dehydration, press the iron and set the reflectance of the cloth to 500mμ.
The re-contamination prevention rate was calculated from the reflectance according to the following equation.

[0058]

(Equation 2)

2. Measurement of Dissolution Rate (Dissolution Rate) of Nonionic Surfactant The method is the same as that described in Example 1, but the content (calculated value) of the nonionic surfactant in the sample of the calculation formula for calculating the dissolution rate is The carry-over from the granular detergent (B) using the anionic surfactant shown in Table 4 as the main cleaning base is removed in advance.

[0060]

[Table 4]

[0061] Note) * 1 sodium dodecylbenzenesulfonate * 2 dodecylbenzenesulfonic acid potassium salt * 3 coconut oil fatty acid composition alkyl ether sulfate sodium salt * 4 C ₁₄ ~C ₁₈ α- olefin sulfonate sodium salt * 5 alpha- Sulfonate fatty acid ester sodium salt (derived from palm oil fatty acid) * 6 Polyethylene glycol (average molecular weight 12000) * 7 Sodium polyacrylate (average molecular weight 5000)

[0062]

[Table 5]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-5100 (JP, A) JP-A-4-339898 (JP, A) JP-A-4-363400 (JP, A) JP-A-4-4 146998 (JP, A) JP-A-62-253699 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 17/06 C11D 1/00-3/60

Claims (17)

(57) [Claims] 1. A powdery or granular detergent composition comprising a nonionic surfactant as a main cleaning base, comprising the following components (a), (b) and (c): (a) One or more nonionic surfactants represented by the following general formulas (1) to (6) having a melting point of 40 ° C. or less: 10 to 40% by weight ・ Formula (1) R -(OR ') _n- OH [wherein, R represents a linear or branched alkyl group having 8 to 20 carbon atoms R'; an alkylene group n having 2 to 4 carbon atoms; and an average value of 3 to 20]. Formula (2) R ″ —CO (OR ′) _n -OR ′ ″ [wherein R ′: an alkylene group R ″ having 2 to 4 carbon atoms; linear or branched having 7 to 19 carbon atoms] Chain alkyl group R ′ ″; hydrogen or alkyl group having 2 to 3 carbon atoms n; average value is 3-20. Formula (3) R- (OR ′) _m -G _p [wherein, R is a linear or branched alkyl group R ′ having 8 to 20 carbon atoms; an alkylene group G having 2 to 4 carbon atoms; Residue m derived from reducing sugar of Formula 5 or 6; average value is 0-5 p; average value is 1-10. [Formula 1] (b) silicon in anhydrous basis contains a SiO ₂ 30 wt% or more, glycerin oil-absorbing ability is represented by 80 ml / 100 g or more on a 5 to 60 wt% oil-absorbing carrier is (c) the following general formula (I) Alternatively, a derivative thereof is contained in a weight ratio of (a) / (c) = 20/1 to 3/1. Embedded image 2. The nonionic surfactant of component (a) is a polyoxyethylene alkyl ether obtained by adding ethylene oxide to a linear or branched alcohol having 8 to 20 carbon atoms with an average addition number of 3 to 15 moles. The cleaning composition according to claim 1. 3. The component (c), p + q + r in the general formula (I)
The cleaning composition according to claim 1, wherein is 0 to 10. 4. The composition according to claim 1, wherein the component (c) is glycerin.
4. The cleaning composition according to any one of items 3 to 3. (5) The component (b) has a 5% dispersion having a pH of 9 or more, or has a solubility of 0.5% in 100 ml of a 2% aqueous NaOH solution.
g or less.
9. The cleaning composition according to item 7. 6. The cleaning composition according to claim 1, wherein the oil-absorbing carrier as the component (b) is an amorphous silica-based substance. 7. The cleaning composition according to claim 5, wherein the oil-absorbing carrier as the component (b) is amorphous silica. 8. The cleaning composition according to claim 5, wherein the oil-absorbing carrier as the component (b) is an amorphous aluminosilicate. 9. An amorphous aluminosilicate represented by the following general formula:
(1) a (M ₂ O) ・ Al ₂ O ₃・ b (SiO ₂ ) ・ c (H ₂ O) (1) (where M is an alkali metal atom, and a, b and c are moles of each component. Represents a number, and 0.7 ≦ a ≦ 2.0, 0.8 ≦ b <4, and c are arbitrary positive numbers. The cleaning composition according to claim 8, which is an amorphous aluminosilicate represented by the formula: 10. The cleaning composition according to claim 1, wherein the content of the alkali metal silicate is 5% by weight or less. 11. The cleaning composition according to claim 1, which has an average particle diameter of 200 to 1000 μm and a bulk density of 0.6 to 1.0 g / cm ³ . 12. A powdery or granular detergent composition (A) comprising the nonionic surfactant according to claim 1 as a main cleaning base, and a main cleaning agent comprising an anionic surfactant. A powder or granular detergent composition comprising the powder or granular detergent composition (B) as a base. 13. A powder or granular detergent composition comprising a nonionic surfactant as a main cleaning base and a powder or granular detergent composition comprising an anionic surfactant as a main cleaning base.
13. The cleaning composition according to claim 12, wherein the weight ratio of (B) is (A) / (B) = 1/99 to 1/1. 14. A powdery or granular cleaning composition (B) containing an anionic surfactant as a main cleaning base comprises the following components (d),
14. The cleaning composition according to claim 12, which is a powdery or granular cleaning composition containing (e) and (f). (d) Sulfonate type anionic surfactant and / or sulfate ester type anionic surfactant 15 to 45% by weight (e) Crystalline synthetic aluminosilicate, crystalline layered silicate and citric acid or One or more divalent metal chelating agents selected from the group consisting of salts thereof 10 to 50% by weight (f) Alkali metal carbonate and / or alkali metal silicate 5 to 40% by weight 15. The powder or granular detergent composition (B) having an anionic surfactant as a main detergent base has an average particle size of 200 or more.
The cleaning composition according to any one of claims 12 to 14, which has a thickness of from 1000 to 1000 µm. 16. The powder or granular detergent composition (B) comprising an anionic surfactant as a main detergent base, which is produced by spray-drying. Cleaning composition. 17. The cleaning composition according to claim 12, which has a bulk density of 0.6 to 0.9 g / cm ³ .