JP3297383B2 - 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 Clothes in which a nonionic surfactant such as an aluminosilicate is added to a detergent containing a liquid to semi-solid nonionic surfactant at room temperature to suppress exudation of the nonionic surfactant. Background of the Invention 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, under alkaline conditions of high pH, the solubility of the detergent after long-term storage may be degraded due to the elution of the silicate compound from the aluminosilicate, for example, SiO ₂ , which may impair the commercial value, such as a decrease in detergency. Was.

[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 significantly improved ability to prevent exudation, detergency and solubility after long-term storage. is there.

[0005]

The present invention comprises the following components (a) to (d), and comprises the components (a) and (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): nonionic surfactant having a melting point of less than 40 ° C. (c): oil absorption capacity measured by JIS K 6220 method of 100 ml / 100 g or more (in terms of anhydrous) )) Alkali-resistant aluminosilicate (d): 10 to 60% by weight of alkali agent

[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 nonionic surfactant [component (b)] having a melting point of less than 40 ° C., for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene sorbitan fatty acid ester, Polyoxyalkylene glycol fatty acid esters and polyoxyethylene polyoxypropylene block polymers are preferred. In particular, polyoxyalkylene alkyl ethers are preferable, and among them, polyoxyethylene alkyl ethers obtained by adding 4 to 20 moles of ethylene oxide on average to alcohols having 10 to 18 carbon atoms are preferable. Also, Griffin
The HLB based on the method n) is preferably 6.5 to 14.0. Melting point is Mettler FP of FP800 Thermo System.
81 (Mettler Instrumente AG)
) At a heating rate of 0.2 ° C / min.

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.

The component (c) of the present invention is JIS K62
Oil absorption capacity measured by the method of No. 20 is 100 ml / 10
It is an alkali-resistant aluminosilicate weighing 0 g or more (in terms of anhydrous content). Here, “alkali-resistant aluminosilicate” means that the amount of SiO ₂ eluted when suspended in a 20% by weight aqueous sodium carbonate solution at 20 ° C. for 16 hours is 30 mg / 10 g or less, preferably 25 mg / 10 g or less, particularly preferably 20 mg / g or less. / 10 g or less of aluminosilicate. Since the aluminosilicate is hardly hydrolyzed even during long-term storage under alkaline conditions, a free silicate compound causing insoluble lumps formed between the powder materials constituting the detergent particles is formed. This is preferable in that the solubility of the detergent composition is significantly reduced. 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 preferred because it has 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 a number from 1.8 to 3.2 and c is a number from 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.

Examples of the alkaline agent of the component (d) include alkali metal carbonates such as sodium carbonate, sodium sesquicarbonate, and sodium hydrogencarbonate, which are collectively referred to as dense ash and light ash, and amorphous amorphous alkali metal. Silicates. For example, water glass such as JIS No. 1, No. 2, and No. 3 sodium silicate, powdered sodium silicate, and a silicate compound in which free silanol (Si-OH) groups are reduced by firing these compounds, for example, Britesil C
20, Britesil H20, Britesil
C24, Britesil H24 (both The P
Q Corporation (registered trademark) and NABIO
A commercially available product such as N15 (RHONE-BOULENC, registered trademark) 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.

Crystalline silicates are particularly preferred in terms of alkali strength, alkali buffering ability and sequestering ability. The crystalline silicate has a maximum pH value of 0.1% by weight or more of a dispersion of 11 or more (at 25 ° C.). Preferably, the amount of the aqueous HCl solution is 5 ml or more.
A crystalline silicate having O ₂ / M ₂ O (where M is an alkali metal atom) of 0.5 to 3.2, particularly 1.5 to 2.6 is preferable.

The crystalline silicate preferably has an average particle size (median size in particle size distribution) of 0.1 to 20 μm, more preferably 1 to 10 μm.

The above crystalline silicate is disclosed in JP-A-5-2790.
No. 13, gazette, column 3, line 17 to column 6, line 24 (particularly 50
A method of firing at 0 to 1000 ° C. for crystallization is preferred. ), JP-A-7-89712, column 2, lower right column, column 1
It can be obtained by the method described in line 8 to page 4, right upper column, line 3 (particularly, silicates in Table 2 are preferable).

The crystalline silicate is available from Clariant under the trade name “Na-SKS-6” (δ-Na ₂ Si _2).
Powders and granules can be obtained as O ₅ ).

Component (d) is 10 to 60% by weight, preferably 15 to 45% by weight, more preferably 2 to 60% by weight in terms of washing performance.
0 to 35% by weight is blended. As the component (d), an alkali agent containing a crystalline silicate is particularly preferred.

The detergent composition of the present invention may 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 cleaning 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.

[0020]

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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. )

[0022]

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(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 indicates 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 good. Molecular weight 1000-8
0000 is suitable. The compounding amount of the copolymer of the formula (X) and / or the homopolymer of the formula (Y) is 1 to 2 respectively.
0% by weight, especially 2 to 10% by weight is preferred.

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 size of the detergent composition of the present invention is preferably from 200 to 1000 μm, particularly preferably from 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 .

[0027]

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.

[0028]

Example 1 <Method of producing detergent> Detergent particles having the composition and the amount shown in Table 1 were produced by any of the following methods.

(1) Production method 1 An aqueous slurry having a water content of 50% by weight was prepared by using components other than amorphous aluminosilicate, enzymes, fragrances and crystalline silicate in an amount of 5% by weight of zeolite and spray-dried. . Next, the mixture was granulated by a screw extrusion granulator to obtain detergent particles.
The granulated particles were placed in a rotary kiln, and 5% by weight of zeolite, an amorphous aluminosilicate, an enzyme, and a crystalline silicate were blended, and a fragrance was simultaneously sprayed to obtain final detergent particles.

(2) Production method 2 7% by weight of zeolite, 3% by weight of AE, aqueous solution having a water content of 50% by weight with each component other than amorphous aluminosilicate, enzyme, fragrance and crystalline silicate A slurry was prepared and spray dried. The obtained spray-dried particles, 3% by weight of AE and 4% by weight of zeolite were charged into a high-speed mixer (stirring tumbling granulator, Fukae Kogyo Co., Ltd.) to perform granulation. Further, 3% by weight of zeolite and amorphous aluminosilicate were added to perform surface modification to obtain a granulated dough. The obtained granulated particles were put in a rotary kiln, and an enzyme and a crystalline silicate were blended, and simultaneously a fragrance was sprayed to obtain final detergent particles.

(3) Production Method 3 An aqueous slurry having a water content of 45% by weight was prepared from each component other than AE, amorphous aluminosilicate, enzyme, flavor, and crystalline silicate, and spray-dried. The obtained spray-dried particles, 4.0% by weight of amorphous aluminosilicate and crystalline silicate were mixed with a Loedige mixer (stirring tumbling granulator, manufactured by Matsuzaka Giken Co., Ltd.).
And stirring was started. AE was added thereto by spraying, and granulation was performed. Next, 2.5% by weight of an amorphous aluminosilicate was added to perform surface modification. The obtained granulated particles were put into a rotary kiln, and the remaining amorphous aluminosilicate and the enzyme were blended, and 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 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 was prepared by attaching an artificially stained liquid having the following composition to the 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 preparing the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth was performed at a gravure roll cell capacity of 58 cm ³ / cm ² , an application speed of 1.0 m / min, a drying temperature of 100 ° C., and a drying time of 1 minute. Cloth is cotton cloth 2003 (made by Tanika Shoten)
It was used. The composition of the artificially contaminated liquid was 0.4% by weight of lauric acid, 3.1% by weight of myristic acid, and 2.% of pentadecanoic acid.
3% by weight, 6.2% by weight of palmitic acid, 0.4% by weight of heptadecanoic acid, 1.6% by weight of stearic acid, 7.8% by weight of oleic acid, 13.1% by weight of triolein, n-hexadecyl palmitate 2 0.2% by weight, squalene 6.5
% By weight, egg white lecithin liquid crystal material 1.9% by weight, Kanuma red clay 8.1% by weight, carbon black 0.01% by weight 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.

[0035]

(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 30 ° C. and a relative humidity of 60.
% For 120 days. After storage, sample a part 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: 10 minutes, stirring method: dissolved under the condition of a magnetic stirrer. Dissolve the solution with an aperture of 74μ
m at a temperature of 105 ° C.
Dried for hours. From the weight of the mesh before and after drying, the residual ratio of the detergent particles was determined by the following formula.

[0037]

(Equation 2)

[0038]

[Table 1]

Hereinafter, each component in Table 1 will be described in detail. LAS: straight chain alkyl (C12-13) sodium benzenesulfonate AS: alkyl sodium (C12-18) sodium sulfate α-SFE: sodium α-olefin sulfonate (C16-18) ・ AE : Polyoxyethylene alkyl (C12 to C1)
6) Average number of moles of ether and ethylene oxide added 9.
5 ・ Soap: Sodium tallow fatty acid ・ Zeolite: 4A zeolite, average particle size 3 μm
(Tosoh Corporation) Amorphous aluminosilicate 1: JP-A-6-179899
Amorphous aluminosilicate obtained according to Synthesis Example B-1 described on page 10 of Japanese Patent Application Laid-Open (JP-A) No. 10-205, 1988. Oil absorption capacity is 285ml / 100g. The amount of SiO ₂ eluted after suspending the amorphous aluminosilicate in a 20% by weight aqueous sodium carbonate solution for 16 hours (25 ° C.) was 6.2 mg / 10 g. Amorphous aluminosilicate 2: Thixorex 25 manufactured by Han France Chemical Co., Ltd. was used. The amount of SiO ₂ eluted after suspending in a 20% by weight aqueous sodium carbonate solution for 16 hours (25 ° C.) is 13
It was 7 mg / 10 g. Oil absorption capacity is 270ml / 100
g.・ Amorphous silicate: No. 1 sodium silicate (Tosoh Corporation)
・ Crystalline silicate: Powder SKS-6 (manufactured by Hoechst Tokuyama Co., Ltd.) pulverized to an average particle size of 50 μm ・ Sodium polyacrylate: Weight average molecular weight of 8000 when polyethylene glycol is used as a standard・ Fluorescent dye: Equivalent mixture of Tinopearl CBS-X (manufactured by Ciba-Geigy) and Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.) ・ 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, as shown in Table 1,
No. 4 has no exudation of the nonionic surfactant and is excellent in solubility even during long-term storage. On the other hand, when the weight ratio of (a) / (b) exceeds 5/1 (Comparative product 1), the detergency against oily dirt is insufficient, and the weight ratio of (a) / (b) is 4 /. When it is less than 6 (Comparative product 2), the exudation of the nonionic surfactant cannot be suppressed. (B) /
If the weight ratio of (c) exceeds 20/1 (Comparative product 3), the exudation of the nonionic surfactant cannot be sufficiently suppressed. Further, when an aluminosilicate having poor alkali resistance is used (Comparative product 4), the solubility after storage is deteriorated, which is not preferable.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C11D 3:12 C11D 3:12 3:10) 3:10) (56) References JP-A-6-179899 (JP, A) JP-A-10-95998 (JP, A) JP-A-10-168483 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-3/60 C11D 17/06

Claims (5)

(57) [Claims] (1) The composition contains the following components (a) to (d),
The weight ratio between component (a) and 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)
(B) / (c) = cleaning composition with 20/1 to 1/5
object. (A): anionic surfactant (b): nonionic surfactant having a melting point of less than 40 ° C
Agent(Polyoxyethylene polyoxypropylene block
Excluding polymer)  (C): absorption measured by the method of JIS K 6220
Oil capacity is 100ml / 100g or more (equivalent to anhydrous)
Lucari resistant aluminosilicate (d): alkaline agent 10-60% by weight 2. The cleaning composition according to claim 1, wherein the component (c) is an amorphous aluminosilicate having the following composition. _{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. ] 3. Component (d) is SiO ₂ / M ₂ O (provided that
3. The cleaning composition according to claim 1, wherein the composition comprises a crystalline silicate having a molecular weight of 0.5 to 3.2. 4. The weight ratio of component (a) to component (b) is (a) / (b) = 5/1 to 1.1 / 1.
4. The cleaning composition according to any one of items 3 to 3. 5. The cleaning composition according to claim 1, wherein the component (a) is selected from an alkyl benzene sulfonate, a sulfate of an alcohol, and a sulfate of an ethoxylated alcohol. .