JP2648074B2 - Tablet type 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 tablet detergent having sufficient strength and improved solubility, which is particularly suitable for washing clothes in an electric washing machine.

[0002]

2. Description of the Related Art There are two types of cleaning agents that are generally used, liquid type and granular type, which improve ease of use such as portability and storage. Therefore, many attempts for tableting have been conventionally proposed.

[0003] These are mainly tablet-type detergents containing an ionic surfactant as a main cleaning surfactant, but tablet-type detergents using a nonionic surfactant as a main cleaning surfactant are also disclosed in, for example, US Patent No. 5,049,027. No. 3,231,506, U.S. Pat. No. 3,247,123, U.S. Pat. No. 3,331,780, U.S. Pat. No. 3,344,076, and the like. These tablet-type detergents have the advantage that they are easier to use than the liquid-type or granular-type detergents described above, but have sufficient strength to withstand handling and transportation, and dissolve quickly when used. In general, when the strength of the tablet is increased by increasing the molding pressure, the solubility in water decreases.

Many proposals have been made to overcome such disadvantages. Among them, for example, after mixing and shaping a decomposition or volatile substance, a method of making it porous by applying a heat treatment, blending a carbonate and a solid acid, and generating carbon dioxide in water There are a method of accelerating dissolution and a method of blending a disintegrant widely used in the field of chemicals to make tablets easily disintegrate in water (JP-B-44-17745, JP-B-47-27208).

However, in these methods, although the solubility in water is improved to some extent, they are not sufficiently satisfactory for practical use. This is because in a tablet containing a large amount of a surfactant such as a detergent, the surfactant hydrates in water and takes on a very viscous property, which makes it difficult for water to enter the inside of the tablet and dissolves. This is because the promotion effect is not sufficiently exhibited.

[0006] Therefore, at present, a tablet detergent satisfying both solubility and tablet hardness has not been found yet.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, using a specific nonionic surfactant as a main surfactant, a porous oil-absorbing carrier, If sodium acetate is blended in a specific range with a composition in which alkali metal carbonate and / or alkali metal silicate is blended in a specific ratio, a tablet detergent improved in both solubility and tablet hardness can be obtained. Find out what you can get,
The present invention has been completed.

That is, the present invention provides the following components (a), (b),
It is intended to provide a tablet-type detergent composition comprising (c) and (d). (a) the average number of moles of added ethylene oxide is 5 to 16, the nonionic surfactant from 10 to 40% by weight of polyoxyethylene alkyl ether having an average carbon number of the alkyl group moiety 10 to 18 (b) oil-absorbing ability 2 to 40% by weight (c) 1 to 30% by weight of an alkali metal carbonate and / or alkali metal silicate (d) 10 to 30% by weight of sodium acetate.

The nonionic surfactant (a) used in the present invention is a linear or linear surfactant having an average alkyl group of 10 to 18 carbon atoms.
Ethylene oxide to branched primary or secondary alcohol
Is added with an average number of moles of added 5 to 16, preferably 7 to 13.
Polyoxyethylene alkyl ether obtained by
You. Such a non-ionic surfactant of the component (a) is used for tablet-type washing.
10 to 40% by weight, preferably 15 to 25% by weight in the agent composition
Are combined. In addition, non-ionic surfactants other than component (a)
It can be blended within the range that does not impair the effects of the present invention.
You. For example, polyoxyethylene alkyl ethers other than (a)
-Tel, polyoxyethylene alkylphenyl ether
, Polyoxyethylene sorbitan fatty acid ester,
Lioxyethylene sorbite fatty acid ester, polyethylene
Len glycol fatty acid ester, polyoxyethylene poly
Lioxypropylene alkyl ethers and the like.
These may be used as a mixture.

The porous oil-absorbing carrier which is the component (b) of the present invention has a pore volume of 50 to 700 c measured by a mercury intrusion method.
It is in the range of m ³ / g. In the present invention, a porous oil-absorbing carrier having an oil-absorbing capacity of 80 ml / 100 g or more is used. As a porous oil-absorbing carrier satisfying such conditions,
An oil-absorbing amorphous silica-based inorganic substance is generally used. For example, Toksil AL-1, Florite RN (manufactured by Tokuyama Soda Co., Ltd.), Nipseal NA (Nippon Silica Industry Co., Ltd.)
), Tixolex 25, Tixosil 38, Zeosil 45 (manufactured by Rhone Plan), Carplex # 100 (Shionogi Pharmaceutical Co., Ltd.)
Manufactured). In particular the following as the porous oil-absorbing carrier general formula _{x (M 2 O) · y} (MeO) · Al 2 O 3 · z (SiO 2) wherein in the present invention, M is an alkali metal atom, Me is an alkaline earth Metal atoms, x, y, z represent the molar ratio of each component, 0.7 ≦ x ≦ 1.
5, 0 ≦ y ≦ 0.1, 1.5 ≦ z ≦ 4.8. It is preferable to use an amorphous aluminosilicate comprising the compound represented by the formula: By using such an amorphous aluminosilicate, a tablet detergent having more excellent solubility can be produced. The method for producing an amorphous aluminosilicate according to the present invention may be a commonly used method, and is not particularly limited. For example, after heating a sodium aluminate aqueous solution, a sodium silicate aqueous solution is gradually added dropwise with stirring. . When calcium is added to the amorphous aluminosilicate, calcium chloride dihydrate may be simultaneously dropped when the aqueous solution of sodium silicate is gradually dropped. After completion of the addition, a heat treatment is performed, and after filtration and washing, the obtained wet cake is dried and pulverized to obtain an amorphous aluminosilicate. The structure of the obtained powder is determined by atomic absorption and plasma emission analysis. The component (b) is incorporated in the tablet-type detergent composition in an amount of 2 to 40% by weight, preferably 5 to 30% by weight.

The component (c) of the present invention comprises at least one selected from alkali metal carbonates and alkali metal silicates.
Species of inorganic salts. For example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate and the like can be mentioned. In the present invention, an alkali metal carbonate is particularly preferred. These inorganic salts preferably have an average particle size in the range of 100 to 1000 μm. The alkali metal carbonate and / or alkali metal silicate as the component (c) is incorporated in the tablet-type detergent composition in an amount of 1 to 30% by weight, preferably 10 to 20% by weight. If the amount of component (c) is less than 1% by weight, the effect of accelerating dissolution cannot be obtained.

The tablet-type detergent composition of the present invention contains (d) 10 to 30% by weight, preferably 10 to 20% by weight of sodium acetate. The effects of the present invention cannot be obtained with salts other than sodium such as potassium acetate. The total amount [(a) + (d)] of the nonionic surfactant (a) and the sodium acetate (d) in the tablet-type detergent composition is preferably 20 to 50% by weight.

[0013] The tablet-type detergent composition of the present invention further has a molecular weight.
By incorporating 2,000 to 30,000 polyethylene glycol in an amount of 0.5 to 10% by weight, preferably 1 to 7% by weight, the storage stability of the tablet is further improved.

The tablet-type detergent composition of the present invention contains an ionic surfactant such as an alkylbenzene sulfonate, an olefin sulfonate, an alkyl ether sulfate, a fatty acid salt, an α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt. Anionic surfactants such as sulfo fatty acid salts can be used, and the counter ions of these active agents include Na, K and ammonium, and preferably Na and K salts. The amount of the ionic surfactant is preferably 5% by weight or less in the tablet-type detergent composition, and is less than 1/3 (weight ratio) of the nonionic surfactant (a), preferably 1 / 5 or less.

In addition to the above components, the tablet-type detergent composition of the present invention comprises a crystalline or non-crystalline synthetic aluminosilicate (A-type zeolite, X-type zeolite, etc.), and JP-A-60-22.
No. 7895 crystalline phyllosilicate, ethylenediaminetetraacetic acid, succinic acid, malic acid, citric acid or salts thereof, carboxylic acid-based polymers such as polyacrylic acid or maleic acid alone or copolymers with other monomers It is desirable to blend a divalent metal ion scavenger such as a water-soluble salt of the above alone or in combination. It is desirable that the divalent metal ion scavenger be incorporated in the tablet-type detergent composition of the present invention in a total amount of 10 to 60% by weight.

[0016] In addition, the tablet-type detergent composition of the present invention contains components normally contained in detergents, for example, a re-contamination inhibitor such as carboxymethyl cellulose, a bleach, an enzyme such as protease, lipase, cellulase and amylase. ,
Antioxidants, fluorescent dyes, fragrances and the like can be added. Further, for example, starch, hydroxypropyl starch, carboxymethylcellulose, hydroxypropylcellulose, crystalline cellulose, which are used in conventional tablet detergents,
Disintegrants such as α-cellulose can also be included.

An example of the method for producing the tablet-type detergent composition of the present invention will be briefly described. The tablet-type detergent composition of the present invention is obtained by gradually adding or spraying a nonionic surfactant to a mixture containing a porous oil-absorbing carrier and an alkali metal carbonate and / or an alkali metal silicate while stirring. Can be easily obtained by further stirring. When polyethylene glycol having a molecular weight of 2,000 to 30,000 is compounded, the amount of polyethylene glycol in the composition is 1%.
It is blended in a mixture containing the above-mentioned porous oil-absorbing carrier and an alkali metal carbonate and / or an alkali metal silicate so as to be 5% by weight. At this time, polyethylene glycol dissolved in water may be used. Further, when a chelate component (crystalline aluminosilicate, tripolyphosphate, citrate, etc.) is blended, it is blended and mixed in the same manner as polyethylene glycol. Tablet type detergent composition of the present invention, after adding a nonionic surfactant, stirring, granulating,
Average particle size 150-1000 μm, preferably 150-700 μm
, And then a granular detergent composition having a bulk density of 0.6 to 1.2 g / cm ³ obtained by adding and mixing a crystalline aluminosilicate (type 4A zeolite) as a coating agent is then tableted. In addition, dissolving is further improved by tableting. (A) ~ in the granular detergent composition in this case
The amount of component (d) is the same as described above, and component (a) is 10 to 40.
% By weight, 2 to 40% by weight of component (b), 1 to 30% by weight of component (c), and 10 to 30% by weight of component (d). Other coating agents include amorphous silica or amorphous aluminosilicate other than the component (b), magnesium carbonate, calcium carbonate,
One or more selected from magnesium silicate, calcium silicate and talc can be used. Particularly preferred are crystalline aluminosilicate, calcium carbonate, amorphous silica or amorphous aluminosilicate other than the component (b). These water-insoluble powder materials have an average particle size of 0.5 to 50 μm,
Preferably those having a range of 0.5 to 30 μm are used. Incidentally, the tablet-type detergent composition of the present invention, usually 1.0 ~
It has a bulk density of 2.0 g / cm ³ .

[0018]

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

Example 1 Zeolite A, sodium tripolyphosphate, various oil-absorbing carriers, sodium citrate, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, 3% by weight of sodium polyacrylate and the amounts shown in Tables 1 to 3 The fluorescent dye is placed in a batch kneader (Irie Shokai Bench Kneader PNV-1), the amount of liquid nonionic surfactant shown in Tables 1 to 3 is gradually introduced, and then 1% by weight of a polyethylene glycol melt is added. Add enzymes and flavors and mix.
A granular detergent composition having the following properties was obtained.

[0020] 10 g of these granular detergent compositions are treated with an inner diameter of 30 mm.
And a tablet-type detergent composition was obtained by applying a pressure of 100 kg / cm ² for 30 seconds. The average particle diameter and specific gravity of the granular detergent composition used for producing the tablet detergent composition were measured under the following conditions, and the results are shown in Tables 1 to 3. 1) Average particle size of granular detergent composition `` RoTap / Model DB No.901001 HEIKO SEISAKUSHO, LTD ''
The average particle diameter of the product was measured according to the method of JIS-K3362, 6, 1. 2) Bulk density of granular detergent composition Measured according to the method of JIS-K3362, 6, 2.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

The hardness and solubility of the tablet detergent composition were evaluated under the following conditions. Table 4 shows the results. 3) Solubility evaluation conditions A two-tub washing machine (Toshiba Galaxy VH-300 S1, without clothing) containing 30 liters of tap water at 20 ° C. was manufactured by the above-described method with the stirring strength set to “strong”. The tablet-type detergent composition is charged. After stirring for 3 minutes, the mixture was drained and the degree of residual state of the tablet-type detergent composition was determined according to the following criteria. Those that do not dissolve within 3 minutes not only tend to remain on clothes even under normal washing conditions, but also cause a reduction in detergency, which is not preferred. Criteria 1; no tablet detergent residue 2; 5 to 10 grains with a diameter of 1 to 3 mm remain 3; about half remains 4; almost remains intact 4) Tablet hardness evaluation conditions Tablets molded under the above conditions Using a digital hardness tester (manufactured by Fujiwara, model number 0240001), the tablet hardness (kg /
cm ²⁾ was measured. If the tablet strength value is not more than 3 kg / cm ² , the tablet type detergent is not preferable because it causes problems such as “cracking” of the tablet.

[0025]

[Table 4]

Note) 1) Nonionic surfactant (I); polyoxyethylene dodecyl ether (average number of moles of ethylene oxide added =
8) 2) Oil-absorbing carrier (a); Toksil NR (Tokuyama Soda Co., Ltd.)
Oil absorption capacity 270 ml / 100 g (measured according to JIS K-5101), average particle diameter 100-150 μm 3) Oil absorbing carrier (b): Method for producing calcium ion-added product / oil absorbing carrier (b) Sodium aluminate aqueous solution ( Na ₂ O 1.55 wt%, Al ₂ O
₃ 2.30% by weight, Na ₂ O / Al ₂ O ₃ = 1.11 (molar ratio)
Was heated to 40 ° C., aqueous sodium silicate solution while stirring at a rotation speed of 1500rpm (Na ₂ O 2.75 wt%, SiO ₂ 7.88 _{wt%, SiO 2 / Na 2 O} = 2.96 ( molar ratio)) 700 g of calcium chloride 1.2 g of dihydrate was reacted dropwise for 20 minutes. After the reaction,
Heat treatment was performed for 15 minutes, followed by filtration and washing.
The obtained wet cake was dried at 105 ° C. and 300 torr for 10 hours and pulverized to obtain an X-ray amorphous aluminosilicate fine powder. As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained amorphous aluminosilicate was as follows: Al ₂ O ₃ = 21.1% by weight, SiO ₂ = 57.2% by weight, Na ₂ O = 2
0.8% by weight and CaO = 0.9% by weight (1.65 Na ₂ O · 0.0
8CaO.Al ₂ O ₃ .4.75 SiO ₂ ). The oil absorption capacity was 210 ml / 100 g.

[0027] 4) ionic surfactants, alkyl (C ₁₂ ~
C ₁₆ ) Sulfate 5) Polyethylene glycol; average molecular weight 15000 6) Sodium polyacrylate; average molecular weight 10000 7) Fluorescent dye / enzyme / fragrance; fluorescent dye (Sumitomo Chemical Co., Ltd.)
(A mixture of cellulase / sabinase / protease = 1/1/1) and 1% by weight, and 0.2% by weight of a common fragrance, for a total of 1.5% by weight. 8) B: Approximate amount of balance to bring the total to 100 9) Nonionic surfactant (II); polyoxyethylene oxide
Decyl ether (ethylene emissions oxide average addition molar number =
20) 10) Oil-absorbing carrier (c); calcium ion-free product ・ Production method of oil-absorbing carrier (c) Sodium aluminate aqueous solution (Na ₂ O: Al ₂ O ₃ = 20.3: 2)
8.2 (weight ratio) 100 parts by weight of sodium aluminate aqueous solution and 2,000 parts by weight of ion-exchanged water are further added. 800 parts by weight of No. 3 water glass solution (commercially available No. 3 water glass)
100 parts by weight) was added dropwise over 20 minutes, and heat treatment was performed at 60 ° C. for 20 minutes, followed by filtration and washing. The obtained wet cake was dried at 120 ° C. for 12 hours and pulverized with a crusher to obtain an amorphous aluminosilicate. As a result of atomic absorption analysis and plasma emission analysis, the composition of the obtained amorphous aluminosilicate was Al ₂ O ₃ = 27.2% by weight, SiO ₂ =
51.2% by weight and Na ₂ O = 21.6% by weight (1.31 Na ₂ O.Al
₂ O ₃ · 3.2 SiO ₂ ). The oil absorption capacity was 200 ml / 100 g.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C11D 3:08 3:10 7:26)

Claims (6)

(57) [Claims] 1. A tablet-type detergent composition comprising the following components (a), (b), (c) and (d). (a) the average number of moles of added ethylene oxide is 5 to 16, the nonionic surfactant from 10 to 40% by weight of polyoxyethylene alkyl ether having an average carbon number of the alkyl group moiety 10 to 18 (b) oil-absorbing ability 2 to 40% by weight (c) Alkali metal carbonate and / or alkali metal silicate 1 to 30% by weight (d) Sodium acetate 10 to 30% by weight 2. A porous oil-absorbing carrier tablet detergent composition according to claim 1 Symbol placement is an amorphous silica-based inorganic materials water insoluble. 3. The tablet-type detergent composition according to claim 2 , wherein the amorphous silica-based inorganic substance is an amorphous aluminosilicate. 4. An amorphous aluminosilicate having the following general formula x (M ₂ O) .y (MeO) .Al ₂ O ₃ .z (SiO ₂ ) wherein M is an alkali metal atom and Me is The alkaline earth metal atom, x, y, z represents the molar ratio of each component, 0.7 ≦ x ≦ 1.
5, 0 ≦ y ≦ 0.1, 1.5 ≦ z ≦ 4.8. The tablet-type detergent composition according to claim 3, comprising a compound represented by the formula: As claimed in claim 4, further component (e), crystalline aluminosilicates, claim 1-4, containing 10-60% by weight of one or two or more selected from tripolyphosphate and citrate
A tablet-type detergent composition according to any one of the above. 6. The composition according to claim 1, wherein the amount of the ionic surfactant is 5% by weight or less in the composition and less than 1/3 (weight ratio) of the nonionic surfactant (a). The tablet-type detergent composition according to any one of claims 1 to 5 .