JP3260122B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cleaning composition.

[0002]

2. Description of the Related Art Anionic surfactants are a major cleaning base compounded in a detergent composition for clothing, and are further used to improve the detergency of organic dirt such as sebum dirt. Activators are often used in combination. Many non-ionic surfactants suitable for this purpose are liquid to semi-solid at room temperature. For this reason, the addition of an oil-absorbing carrier such as aluminosilicate suppressed the exudation of the non-ionic surfactant. Clothing cleaning compositions are known.

[0003] However, although the fluidity is excellent in the initial stage of production, there is a risk that the exudation of the nonionic surfactant during the day is not completely suppressed, or that water-insoluble components are generated when the detergent absorbs moisture. there were. Further, when the detergent after long-term storage is subjected to washing at a high temperature, there is a possibility that undissolved residue may be generated.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a detergent composition in which the non-ionic surfactant has a remarkably improved ability to prevent exudation, detergency and solubility in high-temperature cleaning. is there.

[0005]

The present invention comprises the following components (a) to (c), and comprises component (a) and component (b):
(A) / (b) = 5/1 to 4/6, the total of component (a) and component (b) is 15 to 50% by weight, and the weight ratio of component (b) to component (c) Is (b) / (c) = 20 /
1 to 1/5. (A): Anionic surfactant (b): Ethylene oxide / propylene oxide addition type nonionic surfactant (c): Oil absorption capacity measured by JIS K 6220 method is 100 ml / 100 g or more (in terms of anhydrous). Aluminosilicate

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the anionic surfactant [component (a)], for example, a sulfate ester of an alcohol having 10 to 18 carbon atoms, a sulfate salt of an alkoxylate of an alcohol having 8 to 20 carbon atoms , Alkyl benzene sulfonate, paraffin sulfonate, α-olefin sulfonate, α-sulfofatty acid salt, α-sulfofatty acid alkyl ester salt and the like. Particularly, alkylbenzene sulfonate, sulfate of alcohol and sulfate of ethoxylate of alcohol are preferable. In particular, a linear alkyl benzene sulfonate having 12 to 14 carbon atoms in the alkyl chain and a sulfate ester of an alcohol having 12 to 18 carbon atoms are preferable, and the counter ion is preferably an alkali metal, and particularly preferably sodium and / or potassium. .

As the ethylene oxide / propylene oxide addition type nonionic surfactant [component (b)], for example, an alcohol having 10 to 18 carbon atoms and ethylene oxide (hereinafter referred to as EO) in an average of 4 to 10 mol, propylene oxide (hereinafter referred to as Polyoxyalkylene alkyl ether to which PO) is added in an amount of 0.2 to 5 mol on average. EO and PO may be block polymerization or random polymerization. In particular,
From the viewpoint of improving the cleaning performance, a nonionic surfactant represented by the following general formula (I) is preferable. RO (EO) _x (PO) _y (EO) _zH (I) wherein R is a hydrocarbon group having 10 to 18 carbon atoms,
x, y, and z are average addition mole numbers, respectively, and x> 0,
y = 0.2-5, z> 0, x + y + z = 5-14, x +
z = 4 to 10, and (x + z) / y = 1/1 to 1
0/1. ].

The nonionic surfactant represented by the general formula (I) can be synthesized by blending EO and PO at a molar ratio within the above range. First, EO is reacted first, and then PO is added. After the reaction is completed,
It can be obtained by adding O. The catalysts used for these alkoxylations include, in addition to basic catalysts and acid catalysts, Mg catalysts described in JP-A-7-227540.
O-ZnO, MgO-SnO, MgO-TiO 2, Mg
O-SbO and a catalyst giving a narrow alkylene oxide distribution, such as a similar Mg-based catalyst described in Japanese Patent Application Laid-Open No. 1-164437, etc., may be mentioned.

In the present invention, component (a) and component (b)
Is contained in the composition in a total amount of 15 to 50% by weight, preferably 20 to 40% by weight. In this range, good detergency is obtained, and the degree of freedom in the amount of other components is increased. Component (a) and component (b) are (a) /
(B) = 5/1 to 4/6, preferably 5/1 to 1.1 /
It is blended at a weight ratio of 1. If the weight ratio is less than 4/6, not only the exudation of the component (b) cannot be suppressed, but also the detergency against hydrophilic stains becomes insufficient. On the other hand, when the weight ratio exceeds 5/1, the detergency against oily stains becomes insufficient.

[0010] The component (c) of the present invention is JIS K62.
Oil absorption capacity measured by the method of No. 20 is 100 ml / 10
Aluminosilicate weighing 0 g or more (in terms of anhydrous). The cation exchange capacity is preferably 100 CaCO ₃ mg / g or more.

As the component (c) of the present invention, an amorphous aluminosilicate having the following composition is preferable because of high oil absorption and excellent cation exchange ability. _{a (M 2 O) · Al} 2 O 3 · b (SiO 2) · c (H 2 O) wherein, M is an alkali metal atom, a = 0.7~2, b =
0.8 to 4, c> 0. ] In particular, the following general formula: Na ₂ O.Al ₂ O ₃ .b (SiO ₂ ) .c (H ₂ O) wherein b is 1.8 to 3.2 and c is a number of 1 to 6. . ] Is preferable. The above-mentioned amorphous aluminosilicate can be copied according to the method described in JP-A-6-179899.

In the present invention, the weight ratio of component (b) to component (c) is (b) / (c) = 20/1 to 1/5,
It is preferably 10/1 to 1/4, and this ratio is 20 /
If it exceeds 1, the exudation of the nonionic surfactant cannot be sufficiently suppressed, and if it is less than 1/5, it becomes difficult to produce detergent particles.

The detergent composition of the present invention can contain an alkali agent. Examples of the alkaline agent include alkali metal carbonates such as sodium carbonate, sodium sesquicarbonate, and sodium hydrogen carbonate, which are collectively referred to as dense ash and light ash, and amorphous amorphous alkali metal silicate. For example, water glass such as JIS No. 1, No. 2, and No. 3 sodium silicate, powdered sodium silicate, and silicate compounds in which free silanol (Si-OH) groups are reduced by firing these compounds, for example, Britesil C20,
Britesil H20, Britesil C2
4. Britesil H24 (All The PQ
Corporation, registered trademark) and NABION1
5 (RHONE-BOULENC, registered trademark) or the like can be used. These may be used alone or in combination. Incorporation of an alkaline agent is effective not only in improving the cleaning performance but also in forming the skeleton of the particles when the detergent is dried, and a relatively hard detergent having excellent fluidity can be obtained. The alkali agent is preferably incorporated in an amount of 10 to 60% by weight, particularly 15 to 45% by weight, and more preferably 20 to 35% by weight in terms of cleaning performance.

The detergent composition of the present invention can contain a crystalline aluminosilicate generally called zeolite. As crystalline aluminosilicates, type A, X
Average primary particle size represented by zeolite and p-type zeolite is 0.1
Synthetic zeolites of 10 to 10 μm, preferably 0.1 to 5 μm are suitably used. The crystalline aluminosilicate is preferably present in the composition in an amount of 5 to 50% by weight, more preferably 10% by weight.
４０40% by weight.

The detergent composition of the present invention not only has a function of blocking metal ions, but also has a function of dispersing solid particle stains from clothing and a function of preventing the particles from reattaching (recontamination) to clothing. In this respect, a carboxylic acid-based polymer can be blended. It is preferable to blend a carboxylic acid-based polymer such as a polymer represented by the following formula (X) and / or a polymer represented by the following formula (Y) having a molecular weight of 1,000 to 100,000.

[0016]

Embedded image

Wherein Z is an olefin having 2 to 8 carbon atoms;
A monomer copolymerizable with (anhydride) maleic acid such as acrylic acid, methacrylic acid, itaconic acid, and methallyl sulfonic acid, or a maleic acid salt, and m is a copolymer having a molecular weight of 100
This is a value indicating 0 to 100,000. M is Na, K, NH
₄ , H. )

[0018]

Embedded image

(In the formula, p is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. L is a value such that the molecular weight of the homopolymer is from 1,000 to 100,000. Homopolymers are Na, K, NH
_{It has four} salts. Among these carboxylic acid-based polymers, salts of acrylic acid-maleic acid copolymers and polyacrylates (Na, K, NH ₄ salts) are particularly excellent.
The molecular weight is suitably from 1,000 to 80,000. The compounding amount of the copolymer of the formula (X) and / or the homopolymer of the formula (Y) is preferably 1 to 20% by weight, particularly preferably 2 to 10% by weight.

The detergent composition of the present invention may contain a bleach or a bleach activator. Examples of the bleaching agent include sodium percarbonate, sodium perborate (preferably a monohydrate), and an adduct of sodium hydrogen peroxide. Particularly preferred is sodium percarbonate. When used in combination with the aluminosilicate, it is preferable to coat with sodium borate. The content of the bleach is 0.5 to 12% by weight, especially 1 to 8% by weight.
Is preferred. Examples of the bleaching activator include a transition metal salt or a transition metal chelated with an organic metal chelating agent, an ester or amide compound of a carboxylate, or an organic chlorinated compound. In the present invention, an ester or amide compound of a carboxylate is particularly preferred. Specifically, tetraacetylethylenediamine (TAED), acetoxybenzenesulfonate, JP-A-59-22999, JP-A-63-258647
Or the organic peracid precursor described in JP-A-6-316700. The blending amount of the bleach activator is 0.5
-6% by weight, especially 1-4% by weight is preferred.

The detergent composition of the present invention comprises a crystalline aluminosilicate, a sequestering agent other than a carboxylic acid-based polymer, an acid agent, a bulking agent, a neutral salt, an enzyme, an enzyme stabilizer, a caking inhibitor, Antioxidants, fluorescent dyes, fragrances, defoamers,
Other known detergent components can be blended.

The average particle diameter of the detergent composition of the present invention is desirably 200 to 1000 μm, particularly preferably 200 to 600 μm, in order to obtain preferable powder properties. Further, the bulk density of the cleaning composition of the present invention is 0.5 to 1.2 g / c.
m ³ , preferably about 0.6 to 1.0 g / cm ³ .

[0023]

According to the present invention, it is possible to obtain a detergent composition which does not exude the nonionic surfactant, has excellent detergency, and has excellent solubility even during long-term storage.

[0024]

Example 1 <Method for producing detergent> Detergent particles having the composition shown in Table 1 were produced by the following method. An aqueous slurry having a water content of 50% by weight is prepared by using components other than the amorphous aluminosilicate, the enzyme and the fragrance in an amount of 5% by weight of the zeolite, and spray drying is performed. Next, granulation is performed by a screw extrusion granulator to obtain detergent particles. The granulated particles are put into a rotary kiln and zeolite 5
Weight percent, amorphous aluminosilicate, enzyme blend,
At the same time, a fragrance was sprayed to obtain final detergent particles.

<Evaluation of Performance> (i) Exudation test of nonionic surfactant: length × width × height of 100 mm × 60 m made of 4A filter paper
Fill 200 g of detergent particles in a mx 40 mm box,
Put in a moisture-proof case. After leaving the case in a thermostat at 30 ° C. for one month, the detergent particles are removed from the filter paper box. After the filter paper box is sufficiently blown with air to completely remove the detergent particles, the nonionic surfactant that has permeated the filter paper is extracted using ethanol as a solvent. After adding decanol as an internal standard and concentrating the extract, analysis was carried out by gas chromatography to determine the amount of exuded nonionic surfactant.

(Ii) Detergency test (Preparation of artificially stained cloth) An artificially stained cloth having the following composition was adhered to the cloth to prepare an artificially stained cloth. The artificial contaminant was attached to the cloth by printing the artificial contaminant on the cloth using a gravure roll coater. The step of making the artificially contaminated cloth by adhering the artificially contaminated liquid to the cloth is performed using a gravure roll having a cell capacity of 5
The drying was performed at 8 cm ³ / cm ² , a coating speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. Cloth is cotton gold width 20
03 cloth (manufactured by Tanito Shoten) was used. The composition of the artificial contaminated liquid was 0.4% by weight of lauric acid, 3.1% by weight of myristic acid, 2.3% by weight of pentadecanoic acid, and 6.2 of palmitic acid.
Wt%, heptadecanoic acid 0.4 wt%, stearic acid 1.6 wt%, oleic acid 7.8 wt%, triolein 13.1 wt%, n-hexadecyl palmitate 2.2
% Of squalene, 6.5% by weight of squalene, 1.9% by weight of egg white lecithin liquid crystal, 8.1% by weight of Kanuma red clay, 0.01% by weight of carbon black, and the balance amount of water.

(Cleaning Conditions and Evaluation Method) Five 1 cm × 10 cm artificially-stained cloths prepared as above were placed in 1 liter of an aqueous detergent solution for evaluation, and 100 r was measured with a tergotometer.
pm. The washing conditions were as follows: washing time: 10 minutes, detergent concentration: 0.067% by weight, water hardness: 4 ° DH, water temperature: 20 ° C., rinsing: tap water for 5 minutes. The detergency was measured by measuring the reflectance at 550 nm of the original cloth before and after cleaning and the contaminated cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). Was shown as detergency. The cleaning rate was 60 in this test.
% Is preferable.

[0028]

(Equation 1)

(Iii) Storage solubility test 500 g of detergent particles were filled in a detergent carton (used for attack by Kao Corporation), at a temperature of 20 ° C. and a relative humidity of 60.
% Or a temperature of 40 ° C. and a relative humidity of 60% for 120 days. After storage, a portion was sampled from the top of the filled detergent, dissolved water volume: 1 liter, detergent concentration: 0.067
% By weight, water temperature: 20 ° C., hardness: 4 ° DH, dissolution time: 1
0 minutes, stirring method: Dissolved under magnetic stirrer conditions. The solution was filtered through a metal mesh having a mesh size of 74 μm, and the mesh was dried at 105 ° C. for 1 hour. From the weight of the mesh before and after drying, the residual ratio of the detergent particles was determined by the following formula.

[0030]

(Equation 2)

[0031]

[Table 1]

Hereinafter, each component in Table 1 will be described in detail. LAS: straight-chain alkyl (12 to 13 carbon atoms) sodium benzenesulfonate AS: alkyl (12 to 18 carbon atoms) sodium sulfate AE-1: nonionic surfactant represented by formula (I) (R is an alkyl group having 10 to 14 carbon atoms, x is 2, y
Is 2 and z is 3. AE-2: Nonionic surfactant obtained by randomly polymerizing 10 mol of EO and 2 mol of PO on alcohol having 10 to 14 carbon atoms. AE-3: Nonionic represented by the general formula (I). Surfactant (R is an alkyl group having 6 carbon atoms, x is 2, y is 2, z
Is 3. AE-4: a nonionic surfactant represented by the general formula (I) (R is an alkyl group having 10 to 14 carbon atoms, x is 8, y
Is 3 and z is 5. AE-5: a nonionic surfactant represented by the general formula (I) (R is an alkyl group having 10 to 14 carbon atoms, x is 2, y
Is 6 and z is 3.・ Soap: Sodium tallow fatty acid ・ Zeolite: 4A zeolite, average particle size 3 μm
(Tosoh Corporation) Amorphous aluminosilicate: An amorphous aluminosilicate obtained by Synthesis Example B-1 described on page 10 of JP-A-6-179899. Oil absorption capacity is 285ml / 100g.・ Amorphous silicate: No. 1 sodium silicate (Tosoh Corporation)
・ Sodium polyacrylate: an average weight molecular weight of 8000 with polyethylene glycol as a standard ・ Fluorescent dye: Equivalent mixture of Tinopearl CBS-X (manufactured by Ciba Geigy) and Whitetex SA (Sumitomo Chemical) ・ Enzyme : Sabinase 18.0T Type Whit
e, a mixture of equal amounts of 0.1 T of Cellzyme and 60 T of Termamyl (both manufactured by Novo Nordisk).

(Results) As shown in Table 1, the composition No.
Nos. 1 to 4 have no exudation of the nonionic surfactant and have excellent solubility even during long-term storage. On the other hand, (a) /
When the weight ratio of (b) exceeds 5/1 (Composition No.
5) is insufficient in detergency against oily stains,
When the weight ratio of (a) / (b) is less than 4/6 (composition N
o. 6) cannot prevent the exudation of the nonionic surfactant. When the weight ratio of (b) / (c) exceeds 20/1 (composition No. 7), the exudation of the nonionic surfactant cannot be sufficiently suppressed.

Continuation of front page (72) Inventor Hiroyuki Saijo 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Corporation Laboratory (56) References JP-A-10-95998 (JP, A) JP-A-10-168483 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C11D 1/00-3/60

Claims (2)

(57) [Claims] 1. The composition contains the following components (a) to (d) , and the weight ratio of the component (a) to the component (b) is (a) / (b) =
5/1 to 4/6, the sum of the components (a) and (b) is 1
5 to 50% by weight, the weight ratio of component (b) to component (c) is (b) / (c) = 20/1 to 1/5 , and the content of component (d)
A detergent composition having an amount of 10 to 60% by weight . (A): Anionic surfactant (b): Ethylene oxide / propylene oxide addition type nonionic surfactant (c): Oil absorption capacity measured by JIS K 6220 method is 100 ml / 100 g or more (in terms of anhydrous). Aluminosilicate (d) alkaline agent 2. The cleaning composition according to claim 1, wherein the component (b) is a nonionic surfactant represented by the following general formula (I). RO (EO) _x (PO) _y (EO) _zH (I) wherein R is a hydrocarbon group having 10 to 18 carbon atoms,
x, y, and z are average addition mole numbers, respectively, and x> 0,
y = 0.2-5, z> 0, x + y + z = 5-14, x +
z = 4 to 10, and (x + z) / y = 1/1 to 1
0/1. ]