JP2954487B2 - Nonionic powder detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning composition.
More specifically, the present invention relates to a powder detergent composition containing a nonionic surfactant as a main base, and particularly to a powder detergent composition in which the caking property and dispersibility do not deteriorate during storage under moisture absorption and the bulk density does not decrease.

[0002]

2. Description of the Related Art Nonionic surfactants have good hard water resistance and have good detergency.
It has features such as outstanding dirt dispersing power and very good biodegradability, and is regarded as important as a detergent 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.

Japanese Patent Application Laid-Open No. Sho 50-198113 discloses zeolite,
Or a premix of a finely divided nonionic surfactant on a mixture of a zeolite and an inorganic peroxide that produces hydrogen peroxide in water (even if the premix contains 4% or less highly dispersible silica). Good) 30-100% and spray-dry detergent 0-70%
A fluid detergent containing is disclosed. JP-A-61-
No. 89300 discloses that after mixing a water-soluble powder and silica powder, a nonionic surfactant is sprayed, and then a zeolite powder is added to prepare a granulated material. It is disclosed that a nonionic surfactant-containing granular detergent containing a surfactant-containing granular detergent has good flowability and can prevent caking. The above technology mainly focuses on research on detergent additives containing nonionic surfactants which are subsequently blended into spray-dried detergents using anionic surfactants as the main cleaning base, and nonionic surfactants as the main cleaning base. This cleaning agent has not been sufficiently studied. JP-A-51-41708 discloses a free-flowing detergent composition containing a porous aggregate of a synthetic amorphous silica derivative and a nonionic surfactant.

[0005] As shown in these examples, it is known that silica materials can be used to improve the flowability of detergents containing nonionic surfactants.

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.

[0007] The present inventors have previously identified certain silica derivatives,
It has been found that a nonionic powder detergent composition containing a nonionic surfactant and a zeolite solves the problem of a decrease in solubility over time under these humidifying conditions. On the other hand, the present inventors have found that by adding sodium silicate, the detergency of stains derived from fatty acids can be improved (JP-A-5-202399). Therefore, the specific silica derivative of the former, a nonionic surfactant,
It has been predicted that by adding sodium silicate to a nonionic powder detergent composition containing zeolite and zeolite, the detergency of stains derived from fatty acids can be improved.
However, as a result of various studies based on this finding, when containing a large amount of sodium silicate, such detergents are soluble and dispersible when used under high water temperature conditions such as in the summer, and in the United States and Europe. In addition, a tendency to deteriorate the properties was observed, a high hygroscopic property was exhibited under high-humidity storage, and a tendency to decrease the caking property and the flowability of the detergent powder was observed, and further, a decrease in the bulk density was confirmed. Also JP
No. 55-52396 discloses a technique of mixing a specific soluble sodium silicate as a separate particle into a detergent cloth containing no sodium silicate, but using a nonionic surfactant as a main cleaning base. In this case, the dispersibility was poorer than that of the anionic surfactant, and in a system containing a large amount of a water-insoluble substance such as an oil-absorbing carrier in addition to zeolite, it was not sufficient.

[0008]

Under such circumstances, the present inventors have conducted intensive studies on a cleaning agent containing a nonionic surfactant as a main cleaning base. The silicate and / or alkaline earth metal silicate and the alkali metal carbonate are preliminarily granulated and dry-mixed with a specific powder cleaning composition containing a nonionic surfactant as a main cleaning base, so as to absorb moisture. The present inventors have also found that a powder detergent composition having excellent storage stability and markedly improved caking resistance can be obtained, and the present invention has been completed.

That is, the present invention relates to: (a) a nonionic surfactant having a melting point of 40 ° C. or lower;
Wt%, it contains 5 to 40 wt% silica derivative is (b) oil-absorbing ability 80 ml / 100 g or more, not containing alkali metal silicate content is 5 wt% or less or the alkali metal silicate, the bulk density 650 ~ 1000g / liter,
Nonionic surfactant-supported particles (I) having an average particle size of 320 to 500 μm, and at least 40% of silicon atoms in Q ₂ and Q ₃ forms.
% Of alkali metal silicate and / or alkali earth metal silicate containing at least 20% by weight and 50-80% by weight of alkali metal carbonate containing 300-800% by weight.
non-ionic particles, which are dry-mixed with particles (II) having a particle diameter of μm so that the ratio of particles (I) is 30 to 90% by weight and the ratio of particles (II) is 10 to 50% by weight. The present invention provides a powdery detergent composition.

The nonionic surfactant (a) used in the present invention has a melting point of 40 ° C. or lower, and specific examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl phenyl ether. Ethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene castor oil,
Polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glycoside, alkylamine oxide and the like can be mentioned.

Among them, as a main nonionic surfactant, an alkyl group having 10 to 20, preferably 12 to 18 linear or branched chain, primary or secondary alcohol having an average addition number of 5 to 5 ethylene oxide. It is desirable to use 15, preferably 6 to 12, more preferably 6 to 10, polyoxyethylene alkyl ethers. The component (a) is contained in the nonionic surfactant-supported particles (I) in an amount of from 8 to 50% by weight, preferably
15-40% by weight is blended.

The silica derivative which is the component (b) of the present invention is
Oil absorption capacity measured by the method described in JIS K6220 is 80ml / 10
Those having a weight of 0 g or more, preferably those having a weight of 150 ml / 100 g or more have excellent anti-caking properties. Examples of such silica derivatives include the HSZ series (manufactured by Tosoh Corporation), Toksil (manufactured by Tokuyama Soda Co., Ltd.), and Nipseal (manufactured by Nippon Silica Co., Ltd., Carplex # 10 (Shinogi Pharmaceutical Co., Ltd.)
), SIPERNART D10 (made by Degussa), TIXOLEX 25
(Manufactured by Kofuran Chemical Co., Ltd.). In particular, the component (b) used in the present invention is preferably amorphous, and more preferably an amorphous aluminosilicate represented by the following formula in terms of detergency. _{aMeO · bM 2 O · cSiO 2} · Al 2 O 3 ( in the formula, Me: alkaline earth metal, M: alkali metal, a
= 0-0.1, b = 0.2-2.0, c = 0.5-6) As such an amorphous aluminosilicate, for example, Si
The molar ratio of O ₂ and M ₂ O (M means an alkali metal) is SiO ₂
/ M is ₂ O = 1.0 to 4.0, the molar ratio of between H ₂ O and M ₂ O is H ₂ O
/ M ₂ O = 10~200 a is using the alkali metal silicate solution, to which the molar ratio of M ₂ O and Al ₂ O ₃ is _{M 2 O / Al 2 O 3} = 1.
And 0 to 2.0, the molar ratio of between H ₂ O and M ₂ O is _{H 2 O / M 2 O =} 6.0 ~
An aqueous solution of a low alkali alkali metal aluminate of 500 is added under strong stirring at a temperature of 15 to 60 ° C, preferably 30 to 50 ° C. The resulting white precipitate slurry is then usually treated at a temperature of 70-100 ° C., preferably 90-100 ° C., usually for 10
Heat treatment for not less than 10 minutes, preferably not more than 5 hours,
Thereafter, it can be advantageously obtained by filtration, washing and drying. At this time, the addition method may be a method of adding an aqueous solution of an alkali metal silicate to an aqueous solution of a low alkali alkali metal aluminate. According to this method, an amorphous aluminosilicate oil-absorbing carrier having an ion-exchange capacity of 100 CaCO ₃ mg / g or more and an oil-absorbing capacity of 150 ml / 100 g or more can be easily obtained (JP-A-62-191417, JP-A-62-191417). -191419).

The component (b) is incorporated in the nonionic surfactant-supported particles (I) in an amount of 5 to 40% by weight, preferably 10 to 30% by weight. If the blending amount of the component (b) is less than 5% by weight, the nonionic surfactant cannot be sufficiently supported, and if it exceeds 40% by weight, the caking resistance is reduced.

In the present invention, the content of the alkali metal silicate such as sodium silicate in the nonionic surfactant-supported particles (I) must be 5% by weight or less. More preferably, the content is 1% by weight or less. The reason is,
The alkali of the alkali metal silicate in the nonionic surfactant-supported particles (I) becomes strong alkali-free water under moisture-absorbing storage, and comes into contact with the silica derivative as the component (b) in the particles, resulting in anti-caking properties. ,
This is because the dispersibility is significantly reduced. Of course, it is also possible to use those which do not contain alkali metal silicate in the particles (I).

In the nonionic surfactant-supporting particles (I) containing the components (a) and (b) and having an alkali metal silicate content of 5% or less and a bulk density of 650 to 1000 g / l and an average particle size of 320 to 500 μm. Others include neutral salts, organic builders,
Surfactants other than nonionic surfactants, zeolites, and the like may be included, and these shapes may be any shape such as spouted dough, granular powder, and fine powder. The nonionic surfactant-supported particles (I) are obtained by mixing and stirring all of these powder components, and performing granulation while gradually adding the liquid nonionic surfactant. The production method can be carried out with reference to JP-A-2-209200. At this time, if the component (a) is less than 8% by weight or the component (b) is less than 5% by weight, particles having a bulk density of 650 to 1000 g / liter cannot be obtained. The bulk density of the particles (I) is preferably 7
50-850 g / l, average particle size is preferably 350-42
0 μm.

The nonionic powder detergent composition of the present invention comprises:
The nonionic surfactant-supported particles (I) as described above, and Q ₂
And Q ₃ 20 to 50 wt% of an alkali metal silicate and / or alkaline earth metal silicate in the form of silicon atoms containing at least 40% or more and 50 the alkali metal carbonate
Particles with an average particle size of 300-800 μm containing 80% by weight (II)
Are dry-mixed.

Here, “silicon atoms in Q ₂ and Q ₃ forms”
The term refers to the degree of association of silicon atoms with each other,
“Q ₂ ” means that each silicon atom participates in two —Si—O—Si— bonds and the remaining two bonds are terminal —Si—O—X, where X is an alkali metal or H 2. And “Q ₃ ” means that each silicon atom has two —Si—O—Si
-In addition to the bond, the remainder is terminal -Si-O-X (where X
Is an alkali metal or H 2). In the present invention, an alkali metal silicate is particularly preferred. Q ₂ ,
The content of Q ₃ form of silicon atoms can be determined by NMR and Raman spectroscopy.

As the particles (II), those described in JP-A-4-275400 can be used, and the method for producing the particles can be carried out according to the publication. Particularly, alkali metal silicate and / or alkaline earth A method of adsorbing and / or absorbing an aqueous solution containing 10 to 60% by weight of a dry solid content of a metal silicate on a particulate carrier containing sodium carbonate is preferable. In this case, the silicate expressed on a dry basis / water associating with the silicate is preferable. The weight ratio ranges from 100/120 to 100/40. Further, it can also be produced by granulating an aqueous solution containing silicate by a rotary granulator, densifying it, and drying it. Also,
As the particles (II), a commercially available product such as “NABION 15” (registered trademark, Rhone Poulin Japan KK) can be used. The shape and average particle size of the particles (II) are from 300 to 800 μm, preferably from 400 to 600 μm.

In the particles (II), the SiO ₂ / M ₂ O (M represents an alkali metal) molar ratio of the alkali metal silicate is
It is preferably from 0.5 to 2.0.

The particles (II) may contain 20 to 50% by weight of an alkali metal carbonate. Further, it may contain a surfactant.

The nonionic powder detergent composition of the present invention comprises:
The nonionic surfactant-supported particles (I) as described above
% By weight and particles (II) by dry mixing so as to be 10 to 50% by weight, and has excellent storage stability even under moisture absorption, and remarkably improves caking resistance.
The mixture of the particles (I) and (II) of the present invention does not show a decrease in bulk density even after storage.

The nonionic powder detergent composition of the present invention may contain, as optional components, conventional auxiliary additives such as polyacrylic acid, acrylic acid-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose and the like. Recontamination inhibitor, protease, lipase,
It can contain enzymes such as cellulase and amylase, anti-caking agents such as talc and calcium salts, antioxidants such as tertiary butylhydroxytoluene and distyrenated cresol, fluorescent dyes, bluing agents, and fragrances. Is not particularly limited, and may be blended according to the purpose. Further, when used as a softening detergent, a cationic surfactant or the like, when used as a bleaching detergent, sodium percarbonate,
A small amount of a bleaching agent such as sodium perborate monohydrate or tetrahydrate may be blended with an anionic surfactant or the like when it is desired to increase the mud stain cleaning power.

[0023]

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

Synthesis example : Synthesis of amorphous aluminosilicate aqueous solution of sodium aluminate (Na ₂ O: Al ₂ O ₃ = 21.3: 3
100 parts by weight of 0.2 (weight ratio) aqueous sodium aluminate 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) were added dropwise, and 100 parts by weight were added dropwise, and heat treatment was performed at 60 ° C. for 20 minutes. The obtained wet cake was dried at 150 ° C. for 8 hours, and a pulverized aluminosilicate was obtained with a crusher. Was. The oil absorption capacity of the obtained amorphous aluminosilicate is
The structural formula was 210 ml / 100 g, and the structural formula was confirmed by the elemental analysis of ICP emission analysis as shown below. 1.1 (Na ₂ O) · Al ₂ O ₃ · 3.1SiO ₂ · 5.1H ₂ O Preparation Example of Particles (I) Sodium tallowate 3% by weight, the amount of silica derivative shown in Table 1 and the amorphous shown in Synthesis Examples Aluminosilicate, zeolite, various salts, and 0.5% by weight of fluorescent dye are put into a stirring tumbling granulator (Ladyge mixer), a liquid nonionic surfactant is gradually introduced, and then 2% by weight of a polyoxyethylene glycol melt % Was added to obtain particles (I).

Particles (II) "NABION 15" (registered trademark, Rhone Poulin Japan KK) was used as the particles (II). It has the following physical properties: Average particle size 550 μm Sodium carbonate 55% Sodium silicate (SiO ₂ / Na ₂ O = 1) 29% Water 16% Silicon atom content Q ₀ : 10%, Q ₁ : 10% , Q ₂ : 50%, Q ₃ : 30%, Q ₄ :
Very small amount.

Examples 1 to 9 The particles (I) and the particles (II) obtained in the above production examples were dry-mixed in the proportions shown in Tables 1 and 2, and 0.5% by weight of enzyme and 0.5% by weight of fragrance were added. And the mixture was mixed to obtain final detergent products having the compositions shown in Tables 1 and 2 (Products 1 to 9 of the present invention). Comparative Production Example 1 3% by weight of sodium tallowate, the amount of silica derivative shown in Table 1, and the amorphous aluminosilicate and zeolite shown in the synthesis examples,
0.5% by weight of various salts, particles (II) and fluorescent dye are put into a stirring tumbling granulator (Ladyge mixer), liquid nonionic activator is gradually introduced, and then 2% by weight of polyoxyethylene glycol melt is added. Then, a granulated product was obtained.

Comparative Production Examples 2 and 3 The components shown in Table 2 were granulated in the same manner as in Comparative Production Example 1 to obtain a granulated product.

Comparative Examples 1 to 3 The granulated particles obtained in Comparative Production Examples 1 to 3 were further added with an enzyme 0.1.
5% by weight and 0.5% by weight of perfume were added and mixed to obtain final detergent products having compositions shown in Table 2 (Comparative products 1 to 3).

Evaluation of Detergent The bulk specific gravity of the detergent products obtained in Examples 1 to 9 and Comparative Examples 1 to 3 immediately after production was measured in accordance with JIS K 3362, and the results are shown in Tables 1 and 2. .

The solubility, caking properties, powder fluidity and bulk density of these detergent products were measured by the following methods. Tables 1 and 2 show the results.

(Evaluation method) 1. Solubility test Put 10 g of powder detergent in a sample bottle, and leave the mouth open for 30 minutes.
Leave at 70 ° C. and 70% RH for 3 days. After standing, 1.0 g was sampled, added to 1 liter of tap water at 10 ° C, 30 ° C, 40 ° C, stirred with a magnetic stirrer for 10 minutes, filtered through a 200 mesh (74 µm) wire mesh, and dried. Of the residual amount of filtration (%).

2. Caking property test (1) Using a filter paper (Toyo Filter Paper No. 2), make a box without a top with a length of 10.2 cm, a width of 6.2 cm and a height of 4 cm. Stapling the four corners. (2) Place 50 g of the sample in this box, and put an acrylic resin plate and a lead plate (or iron plate) (total weight 250 g + 15 g) on top of it. (3) This is left in a high-temperature and high-humidity chamber at a temperature of 30 ° C. and a humidity of 80%, and the caking state is determined after 7 days. Judgment of the caking property was performed by obtaining the pass rate as follows.

Passage rate: The sample after the test is gently placed on a wire mesh (or screen, mesh 5 mm × 5 mm), the weight of the powder passing through the wire mesh is measured, and the transmittance of the sample after the test is determined.

[0034]

(Equation 1)

3. Fluidity test of powder and measurement of bulk specific gravity (1) Using a filter paper (Toyo Filter Paper No. 2), make a 10.2 cm long 6.2 cm wide 4 cm high box without a top. Stapling the four corners. (2) Put 50 g of the sample in this box, and put it at a temperature of 30 ° C and humidity of 80
%, And after 7 days, a fluidity test of the powder and a measurement of bulk specific gravity are performed. The flowability test of the powder was performed using the stand and funnel described in JIS K 3362 “Synthetic Detergent Test Method” and the Flow Rate of Metal Powders Flow Rat specified in ASTM B 221348.
Perform measurement according to e. The smaller the value, the better the fluidity. The measurement of bulk specific gravity is based on JIS
The measurement is performed according to K 3362 "Synthetic detergent test method".

[0036]

[Table 1]

[0037]

[Table 2]

Note: In the table, EOp means the average number of moles of ethylene oxide added. * 1 Oil absorption capacity 280ml / 100g * 2 Oil absorption capacity 210ml / 100g

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C11D 17/06 C11D 1/72 C11D 3/08-3/12 WPI / L (QUESTEL)

Claims (5)

(57) [Claims] (1) containing from 8 to 50% by weight of a nonionic surfactant having a melting point of 40 ° C. or less, and (b) from 5 to 40% by weight of a silica derivative having an oil absorption capacity of 80 ml / 100 g or more; A bulk density of 650 with an alkali metal silicate content of 5% by weight or less
Nonionic surfactant-supported particles (I) having an average particle size of 320 to 500 μm, and an alkali metal silicate and / or alkaline earth metal containing at least 40% or more of silicon atoms in Q ₂ and Q ₃ forms. Particles (II) having an average particle diameter of 300 to 800 μm containing 20 to 50% by weight of a silicate and 50 to 80% by weight of an alkali metal carbonate, and having a particle (I) ratio of 30 to 90% by weight, II)
A nonionic powder detergent composition, which is dry-mixed to have a concentration of 10 to 50% by weight. 2. The composition contains (a) 8 to 50% by weight of a nonionic surfactant having a melting point of 40 ° C. or less, and (b) 5 to 40% by weight of a silica derivative having an oil absorption capacity of 80 ml / 100 g or more. And non-ionic surfactant-supported particles (I) containing no alkali metal silicate, having a bulk density of 650 to 1000 g / l, and an average particle size of 320 to 500 μm; and at least 40% or more of silicon atoms in Q ₂ and Q ₃ forms Particles (II) containing 20 to 50% by weight of an alkali metal silicate and / or an alkaline earth metal silicate and 50 to 80% by weight of an alkali metal carbonate and having an average particle size of 300 to 800 μm, ) Is 30-90% by weight, and the particle (II) is
A nonionic powder detergent composition, which is dry-mixed to have a concentration of 10 to 50% by weight. 3. The method according to claim 2, wherein the particles (II) adsorb and / or absorb an aqueous solution containing 10 to 60% by weight of a dry solid content of an alkali metal silicate and / or an alkaline earth metal silicate on a granular carrier of an alkali metal carbonate. 3. The nonionic powder detergent according to claim 1, wherein the weight ratio of the silicate / water associating with the silicate expressed on a dry basis is in the range of 100/120 to 100/40. Composition. 4. The nonionic surfactant of component (a) is a polyoxyethylene alkyl ether having an alkyl group having 10 to 16 carbon atoms and an average addition mole number of ethylene oxide of 5 to 15. The nonionic powder detergent composition according to any one of the above. 5. A component silica derivative of (b) is the following general formula _{aMeO · bM 2 O · cSiO 2} · Al 2 O 3 ( wherein, Me: alkaline earth metal, M: alkali metal, a
= 0-0.1, b = 0.8-2.0, c = 1.8-6) The nonionic powder detergent composition according to any one of claims 1 to 4, which is an aluminosilicate represented by the following formula.