JPH06264099A - Powdery nonionic detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. capable of effectively attaching a fluorescent brightener to clothes to improve the whiteness of the white clothes washed and finished by using predetermined amts. of a specific polyoxyethylene alkyl ether, a specific inorg. compd., a specific polycarboxylic acid, and a specific fluorescent brightener. CONSTITUTION:This detergent compsn. comprises 12-40wt.% polyoxyethylene alkyl ether (A) wherein the average no. of C atom in the alkyl moiety is 10 to 20 and the average no. of moles of added ethylene oxide is 5 to 15: 10-40 wt. % water-insoluble inorg. silica compd. (B) (e.g. an amorphous aluminosilicate) contg. at least 5 wt. % component having an oil absorption of at least 80ml/100 g: 20-50wt.% 8C or lower polycarboxylic acid (salt) (C) (e.g., sodium citrate); and 0.01-1wt.% fluorescent brightener of the formula at a C/B wt. ratio of at least 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is a powder detergent composition in which a liquid nonionic surfactant is a main washing base, and the incorporated fluorescent dye can be effectively attached to clothes in a washing process. The present invention relates to a nonionic powder detergent composition which has a good whiteness after washing of white clothing and the like.

[0002]

2. Description of the Related Art Nonionic surfactants are characterized by good hard water resistance, outstanding cleaning power and stain dispersion power, and very good biodegradability. Therefore, it is regarded as important as a cleaning surfactant.

However, since many nonionic surfactants that are usually used for cleaning are liquid at room temperature,
If a large amount of the liquid detergent is blended into the powder detergent, the nonionic surfactant gradually exudes over time and permeates the inner surface of the paper container, or the fluidity of the powder detergent is significantly impaired. Various investigations have been made because of the problem that the detergent is hardened due to caking and the commercial value is significantly impaired. JP-A-5
0-119813 discloses 50 mg CaO / g (89 mg CaCO ₃
/ G) or more of crystalline aluminosilicate having an ion exchange capacity (4% or less of highly dispersible silicic acid may be used as a simple oil-absorbing agent), a nonionic surfactant and optionally hydrogen peroxide in water. A fluidity-improving detergent containing a spray-dried detergent in a pre-mixture containing an inorganic peroxide to give a solution is disclosed, and JP-A-51-41708 discloses an oil supply capacity of 50 to 200 ml. Disclosed is a detergent composition having improved fluidity, which is obtained by blending a synthetic amorphous silica derivative (including aluminosilicate) of 100/100 g with a nonionic surfactant and a phosphorus-based chelating agent. Japanese Patent Application Laid-Open No. 61-89300 discloses a method for producing a granular detergent having an improved powder physical property, which is produced by mixing a water-soluble powder silica powder, spraying a nonionic surfactant, and adding zeolite or calcium carbonate powder. Is disclosed. Further, Japanese Patent Application Laid-Open No. 5-5100 discloses a compound which causes less exudation and less water-insoluble matter.

However, clothes which have been repeatedly laundered with a powder detergent composition containing a nonionic surfactant as a main detergent base are washed with a powder detergent composition containing another surfactant as a main detergent base. The color of clothing is not as vivid as that of clothing. As a result, the powder detergent composition containing a nonionic surfactant as a main detergent base may cause the user to settle the evaluation that the whiteness of the washed product against white clothing is poor.

The reason why the powder detergent composition containing a nonionic surfactant as the main washing base lacks the vividness of the color of the clothes after washing is due to these nonionic surfactants in liquid form. Exudation of the agent, a system containing a large amount of water-insoluble inorganic substances such as zeolite and an oil-absorbing carrier such as silica used to prevent powder physical properties such as caking, easy to form aggregates in the washing liquid, The fluorescent dye is taken into it, delaying the uniform dispersion of the fluorescent dye, while
As described above, nonionic surfactants have better dispersibility than other surfactants.Therefore, in a system containing a large amount of nonionic surfactants, fluorescent dyes that have not been incorporated into aggregates may be added. Since it is dispersed stably in the washing liquid, it is presumed that the dyeing property of the fluorescent dye on the clothing will be lower than that of the powder detergent composition containing other surfactant as the main washing base. .

Therefore, it has been necessary to consider the formulation of a powder detergent composition in which the effect of the fluorescent dye is sufficiently exerted especially when washing white clothing. However, as for the powder detergent composition containing a nonionic surfactant as the main detergent base,
At present, no studies have been conducted on the improvement of the effect of fluorescent dyes.

[0007]

Under the circumstances, the inventors of the present invention have conducted extensive studies on a powder detergent composition containing a nonionic surfactant as a main detergent base, and as a result,
A powdery detergent composition containing a nonionic surfactant, a water-insoluble silica-based inorganic compound, and a polycarboxylic acid salt having 8 or less carbon atoms in a specific ratio, and a specific optical brightener in a specific ratio. By doing so, it was found that a powder detergent composition having excellent dyeing property of the fluorescent whitening agent to clothing in a powder detergent composition containing a nonionic surfactant as a main washing base can be obtained, and Completed the invention.

That is, the present invention contains the following components (a) to (d), the weight ratio (c) / (b) of the component (b) and the component (c) is 1 or more, and ( b) At least 5% by weight of the components is JIS K
The nonionic powder detergent composition is characterized in that it is a silica-based water-insoluble inorganic compound having an oil absorption capacity of 6220 of 80 ml / 100 g or more. (a) Polyoxyethylene alkyl ether having an average carbon number of the alkyl group portion of 10 to 20 and having an ethylene oxide average addition mole number of 5 to 15% by weight of 40 to 40% (b) a silica-based water-insoluble inorganic compound of 10 to 40 % By weight (c) Polycarboxylic acid having 8 or less carbon atoms or salt thereof 20 to 50
Weight% (d) Optical brightener represented by the following general formula (I) 0.01 to 1
weight%

[0009]

[Chemical 4]

As the component (a) used in the present invention, ethylene oxide is added to a primary or secondary alcohol having 10 to 20 carbon atoms, preferably 12 to 14 carbon atoms, in an average added mole number of 5 to 15, preferably 6. It is desirable to add ~ 10 mol. Also,
The polyoxyethylene alkyl ether generally contains a large amount of ethylene oxide low addition mole number alkyl ether, but 0 to 3 mole addition product is 35 wt% or less, preferably 25 wt% or less. Is desirable.
The component (a) is incorporated in the composition in an amount of 12 to 40% by weight.

The component (b) of the present invention is a water-insoluble silica such as zeolite which is generally used in detergents for improving detergency and porous silica-based oil-absorption carrier for maintaining good powder properties. Although it is an inorganic inorganic substance, at least 5% by weight, preferably 10% by weight or more of the component (b) has an oil absorption capacity of 80 ml according to JIS K 6220 to prevent exudation and caking.
/ 100 g, preferably 100 ml / 100 g or more of a porous oil-absorbing carrier is used. In particular, as a porous oil-absorbing carrier, an amorphous aluminosilicate represented by the following formula (II), which exhibits ion-exchange ability, does not deteriorate the powder physical properties, and the blending amount of component (b) should be reduced. It is preferable because it can x (M ₂ O) ・ y (MeO) ・ Al ₂ O ₃・ z (SiO ₂ ) ・ nH ₂ O (II) (where M is an alkali metal, Me is an alkaline earth metal, x, y, z and n represent the number of moles of each component, 0.2 ≤ x
≤2.0, 0≤y ≤0.1, 0.5 ≤z ≤6.0, and n is an arbitrary number. ) The method for producing the amorphous aluminosilicate represented by the general formula (II) is generally as follows. First, the sodium silicate aqueous solution is added to the sodium aluminate aqueous solution which is being heated and stirred. In some cases, calcium chloride may also be added. After completion of the addition, a heat treatment is performed to obtain a wet cake. An amorphous aluminosilicate can be obtained by drying and pulverizing the obtained wet cake. The amount of each raw material to be added is changed according to the required number of moles of each component.

The component (b) is incorporated in the composition in an amount of 10 to 40% by weight, preferably 10 to 30% by weight. (b) The amount of ingredients
If it is less than 10% by weight, exudation and caking are likely to occur, and if it exceeds 40% by weight, the dyeing property of the fluorescent whitening agent is deteriorated. It should be noted that the smaller the amount of the component (b) in the compounding range specified in the present invention, the better the dyeability of the fluorescent whitening agent.

The component (c) of the present invention is a polycarboxylic acid having 8 or less carbon atoms or a salt thereof, such as tartaric acid, citric acid,
1 selected from succinic acid, oxydiacetic acid, oxydisuccinic acid, tartrate monosuccinate and salts thereof
Or two or more species. The carbon number of the polycarboxylic acid is preferably 4-6. Among these, trisodium citrate and disodium succinate are particularly preferable because they have excellent detergency and are relatively inexpensive. A polycarboxylic acid having 9 or more carbon atoms or a salt thereof does not provide a good effect for the added amount. The component (c) is 20 to 50% by weight in the composition,
It is preferably blended in an amount of 30 to 45% by weight.

In the present invention, the ratio of the component (b) to the component (c) is such that the weight ratio of (c) / (b) is 1 or more, preferably 1.2 or more. If the weight ratio is not 1 or more, good effects cannot be obtained.

The component (d) of the present invention is the fluorescent whitening agent represented by the general formula (I), and the fluorescent whitening agent exhibits excellent fluorescent intensity even with a small amount of dyeing. In addition, the whiteness of the white clothing after the treatment remains stable as compared with other fluorescent whitening agents. The optical brightening agent represented by the general formula (I) is available as "Tinopearl CBS" manufactured by CIBA-GEIGYS. The optical brightener represented by the general formula (I) is contained in the composition in an amount of 0.01 to 1% by weight, preferably 0.05 to
1% by weight is blended.

Examples of the fluorescent whitening agent include those represented by the following general formulas (III) to (XIII) in addition to those represented by the formula (I).

[0017]

[Chemical 5]

[0018]

[Chemical 6]

These optical brighteners have the general formula (I) above.
Since it is less affected by the nonionic surfactant than the fluorescent whitening agent represented by, it is more likely to be dyed on clothing than the fluorescent whitening agent represented by the general formula (I). Satisfactory effects cannot be obtained for the amount of dyeing. However, when it is used in combination with the fluorescent whitening agent of the general formula (I), more excellent fluorescence can be obtained. General formula (III) ~ (XII
When the optical brightener represented by the formula (I) is used in combination, the weight ratio with the optical brightener of the general formula (I) is (I) / [(III) to (XI
II)] = 1/10 to 10/1, and it is preferable to add it in such a range that the total amount of the optical brightening agent in the composition is 0.02 to 2% by weight, particularly 0.05 to 2% by weight.

By adding an acrylic acid-maleic acid copolymer to the nonionic powder detergent composition of the present invention,
Further, the whiteness after washing can be effectively improved. The acrylic acid-maleic acid copolymer used in the present invention has a weight average molecular weight of 20,000 to 200,000, particularly 50,000 to 150.
000 is preferable. The amount of the acrylic acid-maleic acid copolymer compounded in the composition is preferably 0.5 to 10% by weight.

Furthermore, the nonionic powder detergent composition of the present invention contains an ionic surfactant such as an anionic surfactant or a cationic surfactant when it is desired to enhance the detergency of mud stains or impart flexibility. A surfactant may be added, but the amount added is such that the weight ratio of the component (a) to the nonionic surfactant (ionic surfactant) / (nonionic surfactant) is less than 1/4, preferably Is 1/10 or less.

The nonionic powder detergent composition of the present invention contains, in addition to the above-mentioned components, detergent auxiliary agents and additives which are usually incorporated in detergents. Specifically, sodium sulfate, inorganic electrolytes such as sodium carbonate, polyethylene glycol, aminopolyacetate, polyacrylic acid, polyvinylpyrrolidone, carboxymethylcellulose, anti-redeposition agents, and protease, lipase, cellulase,
An enzyme such as amylase, an antioxidant, a bluing agent, a detergent and other commonly used ingredients such as fragrances may be added. Also,
Bleaching agents such as sodium percarbonate, sodium perborate 1 or tetrahydrate, stabilizers of peracids such as sodium borate,
A bleach activator or the like can be used as a cleaning aid.

The powder detergent composition of the present invention comprises a mixture of a component (b) such as a porous oil absorption carrier, a component (c) and an optional powder of an alkali metal carbonate or alkali metal silicate, The nonionic surfactant (a) is gradually added dropwise or sprayed with stirring. The powder detergent composition can be easily obtained by further stirring.

In order to add an ionic surfactant other than the nonionic surfactant to the powder detergent composition, for example, the ionic surfactant and, if necessary, a part of the component (c),
Part of alkali metal carbonate or alkali metal silicate and acrylic acid-to prepare a dry dough by spray-drying an aqueous slurry containing a maleic acid copolymer etc., which is a component (b) such as a porous oil absorption carrier, The nonionic surfactant may be gradually added dropwise or sprayed to the mixture containing the component (c) and the remaining optional components such as alkali metal carbonate or alkali metal silicate while stirring. Even when the ionic surfactant is not blended in the detergent composition, a spray-dried dry material may be used.

The component (d) optical brightener is preferably added slowly when the nonionic surfactant is added by dropping or spraying, and is uniformly dispersed in the powder detergent composition. Also,
The optical brightener may be added as an aqueous solution to the above slurry. The same applies to the case where a fluorescent whitening agent other than the general formula (I) is used in combination.

When a recontamination preventive agent such as polyethylene glycol is blended, the above-mentioned porous oil-absorbing carrier (b) is used.
Component, component (c), may be blended in a mixture containing powder optional components such as alkali metal carbonate or alkali metal silicate, or may be added to the spray-dried dry dough. . At this time, polyethylene glycol dissolved in water may be used.

After adding the nonionic surfactant (a), the mixture is stirred to have an average particle size of 150 to 1000 μm, preferably 150 to 70 μm.
Although particles of 0 μm are obtained, in order to further improve the powder properties of the detergent composition particles, the porous oil-absorbing carrier which is the component (b), that is, amorphous silica, amorphous aluminosilicate, etc. ,
It is desirable to add crystalline aluminosilicate or the like separately to coat the surface of the granular material.

Further, as an agent for improving the physical properties of powder,
(b) In addition to the components, magnesium carbonate, calcium carbonate,
Calcium silicate, magnesium silicate, calcium silicate,
And one or more selected from talc and the like, and the average particle size is 0.5 to 50 μm, preferably 0.5 to 30 μm.
Those in the range of are used.

The nonionic powder detergent composition of the present invention can be obtained by adding these agents for improving the physical properties of powder and then adding post-added components such as enzymes and flavors.

There are no particular restrictions on the apparatus for mixing the nonionic surfactant as long as it is a commonly used stirring machine, but a batch kneader or the like can be used, as disclosed in European Patent No. 513824. By using the method shown, it is possible to obtain a high-density powder detergent composition having a more uniform particle size.

The bulk density of the nonionic powder detergent composition of the present invention thus obtained is about 0.6 to 1.2 g / ml,
It is preferably 0.7 to 0.9 g / ml.

[0032]

The present invention will be further described in the following examples.
The invention is not limited to these examples.

Example 1 (A) Preparation of nonionic powder detergent composition A batch kneader (Irie Shokai Co., Ltd.) was prepared by adding each ingredient in the proportions shown in Table 1.
Bench Kneader PNU-1) into a mixture and add (e)
A polyethylene glycol melt having an average molecular weight of 15,000 was added as a component, and while maintaining the temperature at 40 ° C under stirring, the liquid nonionic surfactant of the component (a) shown in the table was gradually introduced to obtain a particle size of 150-600. A μm powder detergent composition was obtained.

[0034]

[Table 1]

Note) 1) Nonionic activator; polyoxyethylene dodecyl ether (average ethylene oxide addition mole number EO = 8) 2) Nonionic activator; polyoxyethylene dodecyl ether (average ethylene oxide addition mole number EO = 15) 3) Oil absorption carrier; Amorphous silicate "Tokushiru NR" (manufactured by Tokuyama Soda Co., Ltd.) 4) Oil absorption carrier; The oil absorption carrier is a calcium ion-added product, which is produced by the following method. -Method for manufacturing oil absorbing carrier 50% by weight aqueous sodium aluminate solution (Na ₂ O 1.55% by weight, Al ₂ O ₃ 2.3% by weight, Na ₂ O / Al ₂ O ₃ = 1.11 (molar ratio) 1
010 g was heated to 45 ° C and stirred at 1500 rpm while sodium silicate solution (Na ₂ O 2.75 wt%, SiO ₂ 7.8%) was added.
8 wt% was added _{SiO 2 / Na 2 O = 2.96} ( molar ratio) 700 g. Further, 1.56 g of calcium chloride dihydrate was added at the same time. After completion of the addition, heat treatment was carried out at 50 ° C. for 15 minutes, and the obtained wet cake was dried at 120 ° C. and pulverized to obtain about 100 g of amorphous aluminosilicate fine powder.
The powder obtained by X-ray diffraction and atomic absorption and plasma emission analysis was confirmed to be amorphous aluminosilicate (1.7 Na
₂ O ・ 0.1CaO ・ Al ₂ O ₃・ 4.8SiO ₂ ). The oil absorption capacity of the obtained powder was measured according to JIS K 6220 method, and the oil absorption capacity was 200 ml / 100 g.
Met. 5) Oil-absorbing carrier; the oil-absorbing carrier is a calcium ion-free product manufactured by the following method. -Method for manufacturing oil absorbing carrier 50% by weight aqueous sodium aluminate solution (Na ₂ O 1.55% by weight, Al ₂ O ₃ 2.3% by weight, Na ₂ O / Al ₂ O ₃ = 1.11 (molar ratio) 1
010 g was heated to 45 ° C and stirred at 1500 rpm while sodium silicate solution (Na ₂ O 2.75 wt%, SiO ₂ 7.8%) was added.
8 wt% was added _{SiO 2 / Na 2 O = 2.96} ( molar ratio) 700 g. After completion of the addition, heat treatment was carried out at 50 ° C. for 15 minutes, the obtained wet cake was dried at 120 ° C., and pulverized to obtain about 100 g of amorphous aluminosilicate fine powder. The powder obtained by X-ray diffraction and atomic absorption and plasma emission analysis was confirmed to be amorphous aluminosilicate (1.7Na ₂
O ・ Al ₂ O ₃・ 4.9SiO ₂ ). The oil absorption capacity of the obtained powder is JIS K
The oil absorption capacity measured according to the 6220 method was 200 ml / 100 g. 6) Optical brightener (α); “white x SA” manufactured by Sumitomo Chemical Co., Ltd.
, Optical brightener represented by general formula (IV) 7) Optical brightener (β); Ciba-GEIGYS
"Tinopearl CBS", a fluorescent whitening agent represented by the general formula (I) 8) Sodium polyacrylate; weight average molecular weight 8000 9) Acrylic acid-maleic acid copolymer sodium salt; weight average molecular weight 80000 10) Enzyme / fragrance: 1.7% by weight of a mixture of cellulase / savinase / protease = 1/1/1 and detergent common fragrance
0.3 11 ones were formulated wt%) ionic surfactant; alkyl (C ₁₂ -C ₁₆₎ sulfuric acid esters (sodium salt).

(B) Dyeability test Each nonionic powder detergent composition was washed under the following conditions, and the dyeability on clothes after washing and visual judgment by a panelist were carried out. The whiteness of the powder detergent composition after washed with white clothes was evaluated.

<Washing conditions> -Washing machine: Toshiba Galaxy 3.0 kg, washing water = 30 liters of tap water, washing water temperature = 20 ° C, detergent usage = 25 g, washing time 10
Minutes, rinse with running water 8 minutes, dehydration 3 minutes-Drying method; household dryer (Matsushita NH-D40X6) drying time 60 minutes-Clothes used: 1.5 kg, the total amount of the following clothes.・ Types of clothing used: 5 pieces of cotton underwear (manufactured by Gunze Co., Ltd., clothing already comes with optical brightener) → Used for evaluation of dyeability and visual judgment of optical brightener. 5 commercially available cotton blend shirts (polyester / cotton =
65/35, clothing is pre-attached with optical brightener) → Used for visual evaluation. Cotton cloth (not treated with optical brightener) → 10cm × 10cm
Gold Width # 2023 cloth. Used to evaluate the dyeability of optical brighteners.

<Evaluation of dyeing property of fluorescent whitening agent on laundry clothes>
IF value is measured using a colorimeter 300 A manufactured by Nippon Denshoku Co., Ltd. That is, the IF value of the clothes before washing and the IF value of the clothes after 5 times of washing were measured, and the dyeing property of the fluorescent whitening agent was evaluated by the difference in IF. Table 2 shows ΔIF (difference between the IF value of clothes before washing and the IF value of clothes after 5 times of washing). The larger ΔIF is, the better the dyeability of the fluorescent dye to the clothing is, and it is evaluated by the following visual determination that the laundry clothing is finished whiter and more vividly. Generally, the undyed cloth has an IF value of almost 0 before washing. The IF values of underwear and cotton cloth before washing are underwear of 18.3 and cotton cloth of 0.3.

<Visual Judgment of Whiteness of Laundry Clothes by Paneler> The whiteness of clothes before and after washing 5 times is compared. That is, the standard light source device (suga tester
(Manufactured by Co., Ltd.), the whiteness of the clothing for visual judgment before and after washing under natural light and a light source of a fluorescent lamp is compared by a panel (5 persons) according to the following evaluation points. 3: Compared to clothes before washing, clothes after washing have a whiter finish. 2 ... Compared to clothes before washing, clothes after washing have the same finish. 1 ... Compared to the clothes before washing, the clothes after washing have a poor finish. The total score of all panelists is shown in Table 2. In this evaluation, the higher the total score is, the whiter the laundry clothes are. The higher the number, the more visually the clothes are white. appear. When the total score of the visual determination results is 9 or less, the finish after washing is not as good as that of unwashed clothes.

[0040]

[Table 2]

Claims (5)

[Claims] 1. The following components (a) to (d) are contained, the weight ratio (c) / (b) of the component (b) and the component (c) is 1 or more, and
(b) A nonionic powder detergent composition characterized in that at least 5% by weight of the component is a silica-based water-insoluble inorganic compound having an oil absorption capacity according to JIS K 6220 of 80 ml / 100 g or more. (a) Polyoxyethylene alkyl ether having an average carbon number of the alkyl group portion of 10 to 20 and having an ethylene oxide average addition mole number of 5 to 15% by weight of 40 to 40% (b) a silica-based water-insoluble inorganic compound of 10 to 40 % By weight (c) Polycarboxylic acid having 8 or less carbon atoms or salt thereof 20 to 50
Weight% (d) Optical brightener represented by the following general formula (I) 0.01 to 1
% By weight 2. Further, as the component (e), the weight average molecular weight is
The nonionic powder detergent composition according to claim 1, which contains 0.5 to 10% by weight of an acrylic acid-maleic acid copolymer having a content of 20000 to 200,000. 3. The nonionic powder detergent composition according to claim 1 or 2, wherein the silica-based water-insoluble inorganic compound (b) is an amorphous aluminosilicate represented by the following general formula (II). x (M ₂ O) ・ y (MeO) ・ Al ₂ O ₃・ z (SiO ₂ ) ・ nH ₂ O (II) (where M is an alkali metal, Me is an alkaline earth metal, x, y, z and n represent the number of moles of each component, 0.2 ≤ x
≤2.0, 0≤y ≤0.1, 0.5 ≤z ≤6.0, and n is an arbitrary number. ) 4. The optical brightener represented by the following general formulas (III) to (XIII) is added in an amount of 1/10 to 10/1 with respect to the optical brightener represented by the general formula (I). The nonionic powder detergent composition according to any one of claims 1 to 3, which is contained in a weight ratio and contains 0.01 to 2% by weight of the optical brightener in a total amount in the composition. [Chemical 2] [Chemical 3] 5. The content of the ionic surfactant in the composition is 5% by weight or less, and the content of the ionic surfactant is 5% by weight or less.
The powder detergent composition according to any one of claims 1 to 4, wherein the weight ratio of (a) to the nonionic surfactant is less than 1/4.