JPH06192697A - High-bulk-density granular detergent composition - Google Patents

Abstract

PURPOSE:To obtain a high-bulk-density granular detergent compsn. extremely excellent in enzyme stability during storage thereof. CONSTITUTION:A detergent compsn. is a blend comprising (a) anionic base particles contg. 5-40wt.% anionic surfactant, (b) nonionic base particles contg. 5-50wt.% nonionic surfactant, and (c) an enzyme. The wt. ratio of the anionic surfactant derived from the anionic base particles to the nonionic surfactant derived from the nonionic base particles is in the range of 9/1 to 5/5, and the total amt. of the surfactants is 5 to 50wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high bulk density granular detergent composition which is extremely excellent in enzyme stability during storage.

[0002]

2. Description of the Related Art Conventional laundry detergents contain a bulking agent having a bulk density of 0.1% by adding an extender (usually Glauber's salt) that hardly contributes to the cleaning performance to the composition and spray-drying it.
It was produced as bead-shaped hollow particles of about 3 g / cc. However, since such detergents have a low specific gravity and a low concentration of activator, they are costly to transport and require a large amount of space for storage and display. It was Therefore, recently, a method for producing a high bulk density granular detergent which can be washed with a small amount of detergent has been proposed (JP-A-60-96698).
No. gazette), and is also on the market. In addition, an enzyme is often added in order to further improve the detergency, but in this case, there is a drawback that the enzyme activity decreases with time.

[0003]

SUMMARY OF THE INVENTION The present invention is directed to improving enzyme stability during storage of high bulk density granular detergent compositions.

[0004]

The high bulk density granular detergent composition of the present invention comprises: (a) Anionic base particles containing 5 to 40% by weight of anionic surfactant. (B) 5 to 5% of nonionic surfactant. 50% by weight of nonionic base particles (c) A mixture of an enzyme and (a) anionic surfactant derived from anionic base particles of component (a) and (b) nonionic base particles. (B ') derived nonionic surfactant is included in a weight ratio of (a') / (b ') = 9/1 to 5/5, and (a') and (b ') are added together. 5 to 50 in quantity
It is characterized by containing by weight%.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The high bulk density granular detergent composition of the present invention comprises (a) anionic base particles containing 5 to 40% by weight of anionic surfactant and (b) 5 nonionic surfactants.
To 50 wt% of nonionic base particles are powder-mixed, and further contains (c) enzyme and has a bulk density of 0.5 to
It is 1.2 g / cc. The enzyme (c) may be incorporated into the base particles of (a) or (b), (a),
The base particles of (b) may be separately powder-mixed.

In the final high bulk density granular detergent composition, the (a ') anionic surfactant contained in the anionic base particles of the component (a) and the nonionic base particle of the component (b) are contained. (B ') nonionic surfactant
(A ′) / (b ′) = 90/1 by weight in the detergent composition
It is blended in the range of 0 to 50/50, preferably 80/20 to 60/40. If the compounding ratio deviates from this range,
The desired enzyme stability cannot be obtained. Further, the (a ') anionic surfactant and the (b') nonionic surfactant are
The total amount (a ′) + (b ′) = 5 to 50% by weight, preferably 15 to 40% by weight. If the blending amount is less than 5% by weight, sufficient detergency cannot be obtained, while if it exceeds 50% by weight, production becomes difficult.

Specific examples of the (a ') anionic surfactant in the anionic base particles of the component (a) include the following. (1) α-sulfo fatty acid ester salt represented by the following chemical formula 1 or di salt of fatty acid sulfonate,

[0008]

[Chemical 1] (R: alkyl group or alkenyl group having 8 to 20 carbon atoms Y: alkyl group having 1 to 3 carbon atoms or counter ion Z: counter ion)

(2) A linear alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16, (3)
Α-olefin sulfonate having an average carbon number of 10 to 20,
(4) Alkyl sulfate having an average carbon number of 10 to 20,
(5) Having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20, and an average of 0.5 to 8
Alkyl ether sulphate or alkenyl ether sulphate having added moles of ethylene oxide, (6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22. As the counterion in the above anionic surfactant,
Usually, alkali metal salts such as sodium and potassium are suitable. These anionic surfactants may be used alone or in combination of two or more.

In the anionic base particles of the component (a), in addition to the anionic surfactant, an inorganic builder such as zeolite (aluminosilicate), sodium tripolyphosphate or sodium pyrophosphate; sodium citrate,
Calcium ion scavenging builders such as sodium ethylenediamine tetraacetate, nitrilotriacetic acid salt, sodium polyacrylate, sodium acrylate-sodium maleic anhydride copolymer, polyacetal carboxylate;
Alkali builders such as carbonates and silicates; Anti-redeposition agents such as carboxymethyl cellulose and polyethylene glycol; Viscosity modifiers such as paratoluene sulfonate, toluene sulfonate, xylene sulfonate, urea; Proteases, lipases, cellulases An enzyme such as amylase (in particular, an alkaline lipase having an activity in an alkaline atmosphere); a softening agent such as a quaternary ammonium salt or bentonite; a bleaching agent, a fluorescent agent, a fragrance, or a dye can be used. Of these, those that can be blended as granules, such as enzymes and bleach,
It is preferable to powder mix the (a) anion base particles and the (b) nonion base particles. Further, the nonionic surfactant can be blended in the (a) anion-based particles as long as the effects of the present invention are not impaired. (A) The amount of the nonionic surfactant incorporated into the anionic base particles is 1
Less than 0% by weight is preferred.

The (a) anionic base particles of the present invention are obtained by granulating each of the above components to obtain base particles having an average particle size of 200 to 1000 μm and a bulk density of 0.5 to 1.2 g / cc. can get. As this granulation method, the above-mentioned JP-A-60 is used.
As described in JP-A-96698, a detergent raw material such as an anionic surfactant is kneaded and mixed with a kneader, crushed and granulated by a crusher such as a cutter mill type, and further mixed with a water-insoluble fine powder. It is obtained by doing. Alternatively, a part or all of the detergent components may be previously spray-dried, and the spray-dried product and the remaining detergent components may be kneaded and mixed to produce the (a) anion-based particles. Alternatively, the (a) anion-based particles can be produced by stirring and granulating the spray-dried particles and other detergent components.

Examples of the nonionic surfactant (b ') in the nonionic base particles of the component (b) of the present invention include the following. (1) Alcohol ethoxylate obtained by adding ethylene oxide to alcohol (2) Alcohol alkoxylate obtained by adding ethylene oxide and propylene oxide to alcohol (3) Fatty acid ester type nonionic surfactant represented by Chemical formula 2

[0013]

[Chemical 2] (R₁CO: Long-chain fatty acid residue R₂: C2-C4 alkylene group R₃: Lower alkyl group)

(4) Nonylphenol ethoxylate obtained by adding 5 to 20 mol of ethylene oxide to nonylphenol on average (5) Fatty acid alkanolamide (6) Sucrose fatty acid ester (7) Alkylamine oxide (8) Sugar represented by the following chemical formula 3 Fatty acid ester-based surfactant

[0015]

[Chemical 3] (R _{1 is} a linear or branched alkyl or alkenyl group having 5 to 17 carbon atoms R ₂ : hydrogen atom or an alkyl group having 1 to 4 carbon atoms) (9) Alkyl glycoside represented by the following chemical formula 4

[0016]

Embedded image RO (R′O) y (Z) x (Z: a residue derived from a reducing sugar having 5 to 6 carbon atoms R: an alkyl group, an alkenyl group, an alkylphenyl group,
A hydroxyalkyl group, a hydroxyalkylphenyl group or a mixture thereof, wherein the alkyl group or the alkenyl group has 8 to 20 carbon atoms R ': an alkylene group having 2 to 4 carbon atoms y: 0-30 x: 1.0 ~ 1.42)

Examples of the sugar residue Z include monosaccharides such as glucose, galactose, xylose, mannose, lyxose and arabinose, and polysaccharides such as maltose, xylopyose, lactose and sucrose. Among the above-mentioned nonionic surfactants, particularly saturated or unsaturated aliphatic primary or secondary having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms.
Average 10 to 30 mol, preferably 12 to
Alcohol ethoxylates with 20 moles of ethylene oxide added are preferred, especially alcohol ethoxylates with ethylene oxide added to aliphatic primary alcohols. Further, as the nonionic surfactant, the ester type nonionic surfactant represented by Chemical formula 5 below is also suitable.

[0018]

[Chemical 5] (R₁CO: 6 to 22 carbon atoms, preferably 10 to 1 carbon atoms
8 saturated or unsaturated fatty acid residues, linear
May be a branch R₂: C 2-4, preferably C 2 alkylene group R₃: C1-4 alkyl group n: OR₂Shows the average number of added moles of 5-30, preferably
(N = 7 to 20)

The above ester type nonionic surfactant is
Structurally, it is an alkyl ether of an alkylene oxide adduct of a fatty acid, and can be obtained by a two-step method such as adding an alkylene oxide to an alcohol by a conventional method and then esterifying with a fatty acid. ) Ion, gallium (Ga) ion, indium (In) ion, thallium (Tl) ion, cobalt (Co) ion, scandium (Sc) ion, lanthanum (La) ion, and divalent manganese (Mn) ion. Those produced by a one-step method of reacting a fatty acid alkyl ester R ₁ COOR ₃ with an alkylene oxide in the presence of a catalyst made of magnesium oxide to which one or more metal ions are added are preferred (Japanese Patent Application No. 3-103).
63904). These nonionic surfactants may be used alone or as a mixture in an appropriate ratio.

The nonionic base particles of the component (b) have a particle size of 5
It is preferable that the particles of about 0 to 1000 μm are mixed with the nonionic base particles of the component (a). The nonionic base particles of the component (b) can be granulated by using an appropriate carrier. For example, after mixing a water-soluble inorganic compound and silica powder, the mixture is sprayed with a nonionic surfactant,
Then, it is obtained by adding a coating agent such as zeolite and granulating. As the water-soluble inorganic compound,
Powders of water-soluble builders for detergent addition such as sodium carbonate, sodium sulfate and sodium citrate are preferred,
These may be used alone or in combination. A suitable average particle size of these powders is 100 to 500 μm. Further, the silica powder preferably has a particle size of 0.1 μm or less.

As the enzyme (c), a hydrolase, a transferase, an oxidoreductase, etc., which has an optimum pH and an optimum temperature range under the use conditions of the detergent composition and exerts an enzymatic activity during washing, is used. However, hydrolases such as protease, lipase, amylase and cellulase are preferred. For example, as the protease, alcalase, sabinase (Novo Industry Co., Ltd.), alkaline protease (Takeda Chemical Industry Co., Ltd.), bioplase (Nagase Industry Co., Ltd.), Esperase (Novo Industry Co., Ltd.), Matsurase (Matsutani Chemical Co., Ltd.), Maxatase (Gist Procades Co., Ltd.) ),
Pronase (Kaken Kagaku), Protin (Daiwa Kasei) and the like can be mentioned.

As the lipase, Candida cy
Lindracea, Humicola lanugi
nosa, Psudomonas, Mucor s
p. , Chromobacterium viscos
There are microbial origins such as um and Rhizopus japonics, and lipase MY, lipase OF (above, manufactured by Meito Sugar Industry Co., Ltd., origin Candida cyli
ndracea), lipase CE (manufactured by Amano Pharmaceutical Co., Ltd.,
Origin Humicola lanuginosa), lipase P, lipase CES (above, Amano Pharmaceutical Co., Ltd., origin Pseudomonas), lipase SP (Novo, origin Mucor sp.), Lipolase (Novo, Aspergillus or by gene recombination).
manufactured by yzae), lipase (manufactured by Toyo Brewing Co., Ltd., origin Chromobacterium viscosu)
m), lipase LPL (manufactured by Oriental Yeast Co., Ltd.),
Olipase (Osaka Bacteria Research Institute, origin Rhizopus
Japanes), lipase B (manufactured by Sapporo Breweries Ltd., origin Pseudomonas) and the like.

As amylase, α-amylase (Midwest Biochemical Co., USA), α-amylase (Nagase Sangyo), α-amylase (Warrellstein, USA), amylase preparation (Rohm and Haas Co., Ltd.) ), Bacterial α-amylase A, BAN (Novo.
Industry Co., Ltd., Bio-Crytase (Daiwa Kasei), Clarase (Miles Laboratory Co., Ltd.), Fangal Mill (Novo Industry Co., Ltd.), Maxsazyme FA (Guinness Progedez Co., Ltd.), Spitase (Nagase Sangyo), Termamine (Novo. (Industry company) and the like are commercially available. Of these enzymes, protease and lipase are preferably used. The enzyme (c) is preferably blended as a granulated product in the high bulk density granular detergent composition.

[0024]

EFFECT OF THE INVENTION According to the present invention, the detergent base particles containing the anionic surfactant and the base particles containing the nonionic surfactant are powder-mixed at a specific ratio, so that the storage stability of the enzyme is good. A high bulk density granular detergent composition is obtained.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but prior to this, the evaluation methods adopted in the examples will be described.

(1) Method for evaluating enzyme stability After filling a practical carton with 750 g of the detergent composition and sealing the mixture, 25 ° C.-60% RH × 8 hours and 35 ° C.-85% R
After being stored for 40 days in a room in which the conditions of H × 16 hours are alternately repeated, the residual activities of lipase and protease are measured and the enzyme stability is evaluated as follows.

(I) Method for measuring lipase activity Using olive oil as a substrate, fatty acids liberated by the lipase action are quantified by alkali titration, and the lipase activity is determined from the value. As the enzyme unit, one unit is an enzyme that releases 1 μM fatty acid per minute from the substrate olive oil at 37 ° C. Olive oil emulsion (4 ml) and 0.1 M phosphate buffer (pH 7.0) (4 ml) are accurately placed in a 50 ml stoppered Erlenmeyer flask, mixed well, and preheated for 10 minutes using a constant temperature water bath at 37 ° C. To this, 1 ml of the sample solution was accurately added, mixed well, and after exactly 20 minutes, an acetone / ethanol mixed solution was added. Then, titration is performed with a 0.05N sodium hydroxide reagent solution using 5 drops of a phenolphthalene solution as an indicator. Separately, 5 ml of olive oil emulsion and 4 ml of 0.1M phosphate buffer (pH 7.0) were accurately placed in a 50 ml Erlenmeyer flask with stopper, heated at 37 ° C. for 30 minutes, poured with 20 ml of acetone / ethanol mixture, and then 1 ml of sample solution. Is accurately added and titrated with 0.05N sodium hydroxide test solution using 5 drops of the ethanol solution of fethanolphthalene as an indicator to give a control solution. The lipase titer is calculated according to the following formula 1 and the residual activity is calculated.

[0028]

[Equation 1]

(Ii) Protease residual activity measurement method Adjustment of substrate 1 to 1.2 g of Hanmusten casein (manufactured by Merck)
Add N-NaOH and swell by stirring well. Then 0.
Add 160 ml of 05M boric acid and stir with a stirrer.
After adjusting the pH to 10.5, make up to 200 ml. Procedure Put 2 ml of sample solution into the test tube. 5 ml of the substrate solution previously heated to 37 ° C. is placed in a test tube on the sample side, stirred for 10 seconds with a flash mixer, and then placed in a 37 ° C. water bath. After reacting for 30 minutes, 0.44M trichloroacetic acid solution 5
Add ml to stop the reaction. After standing for 30 minutes, filtration is performed. On the blank side, 2 ml of the sample solution is placed in a test tube, 5 ml of the trichloroacetic acid solution is added, and then 5 ml of the substrate solution is added, and the same treatment as the sample side is performed. The absorbance of the filtrate at 275 nm is measured using a spectrophotometer, and the difference in absorbance between the sample side and the blank side is determined. The residual activity is calculated from the following formula 2.

[0030]

[Equation 2]

Example 1 (1) Preparation of Anion-Based Particles Using the components excluding the nonionic surfactant, a part of zeolite, and a part of sodium carbonate from the composition of anion-based particles shown in Table 1 below. , A detergent slurry having a solid content of 45% was prepared. This detergent slurry was dried at a hot air temperature of 380 ° C. to a water content of 5% using a countercurrent spray drying tower to obtain a spray-dried product. This spray-dried product has an average particle size of 3
The flowability was also good with 50 μm, bulk density of 0.35 g / cc, and angle of repose of 45 degrees. Then, the dried product, nonionic surfactant and water were continuously kneaded (Kurimoto Iron Works, KR
C kneader # 2) to obtain a dense and uniform kneaded product. A perforated plate (thickness 10 mm) having 80 holes with a diameter of 5 mm was installed at the outlet of this kneader, and the kneaded product was about 5 mm.
φ × 10 mm cylindrical pellet was prepared. The pellets were introduced into a crusher (speed mill ND-10 type, Okada Seiko Co., Ltd.) together with double the amount (weight ratio) of cooling air at 15 ° C. The crusher has a cutter with a length of 15 cm in four stages of cross, rotates at 3000 rpm, the screen is made of punching metal 360 degrees, and the hole diameter is 20 mmφ,
The aperture ratio is 20%. For particles that have passed through the screen,
Anionic base particles (A having a composition shown in Table 1 below and having a bulk density of 0.95 g / cc) were prepared by mixing 6.5% by weight of finely divided sodium carbonate and 2% by weight of A-type zeolite powder. ~ E) was obtained.

(2) Preparation of Nonionic Base Particles In the constitution shown in Table 2, average particle diameter 300 to 350 μm
m sodium carbonate powder and average particle size 0.01 to 0.0
3 μm silica powder was uniformly mixed. Next, while spraying the above mixture with a nonionic surfactant, it is tumbled and granulated by a drum type granulator, and further, A-type zeolite having an average particle size of 1 to 2 μm is added and coated to coat the nonionic base particles (A to O). ) Got.

(3) Preparation of High Bulk Density Granular Detergent Composition Anion-based particles and nonionic-based particles obtained as described above were powder-mixed in a ratio shown in Table 3 and the enzyme and Sample No. with fragrance added. High bulk density granular detergent compositions 1 to 11 (bulk density 0.6 to 1.2 g / cc) were obtained.

[0034]

[Table 1] Table 1: (a) Anion-based particle sample No. ABCDE Component (wt%) α-SF-Na * ¹ 20 8 15-30 AOS-K * ² 3 10 4 --- LAS −K * ³ − 10 4 22 − LAS-Na * ⁴ − 7 − − − AS-Na * ⁵ − − 2 10 − AES-Na (p = 3) * ⁶ − − 2 − − Soap * ⁷ 4 4 4 4-Polyacrylic acid Na * ⁸ 1 1 1 1 1 1 Zeolite (4A type) 20 20 20 20 20 Sodium silicate − 4− 4-Sodium carbonate 10 10 10 10 10 Potassium carbonate 5 5 5 5 5 Sodium sulfate 27 12 23 14 10 Sodium sulfite 2 2 2 2 2 Tinopearl CBS-X * ⁹ 0.2 0.2 0.2 0.2 0.2 Nonionic surfactant (AE) * ¹⁰ 2 2 2 2 2 Water Remainder Remainder Remainder Remainder * 1) α-SF-Na: Carbon Number 12-14 / carbon number 1
Sodium sulfonate of saturated fatty acid methyl ester in a ratio of 6 to 18 = 3/7 * 2) AOS-K: C _{14 to} C ₁₈ potassium α-olefin sulfonate * 3) LAS-K: linear alkyl (C ₁₀ -C ₁₄₎ potassium benzenesulfonate * 4) LAS-Na: a linear alkyl (C ₁₀ ~C ₁₄₎ sodium benzenesulfonate * 5) AS-Na: sodium alkyl sulfate C ₁₂ ~C ₁₈ * 6) AES- Na (P = 3): polyoxyethylene C _{12 to} C ₁₈ sodium alkyl ether sulfate (addition of 3 mol of ethylene oxide on average) * 7) Soap: C _{14 to} C ₁₈ saturated fatty acid sodium * 8) Polyacrylic acid Na: poly sodium acrylate, MW = 5000 * 9) fluorescent whitening agent (manufactured by Ciba-Geigy) * 10) nonionic surfactant (AE): C ₁₂ alcohol ethoxylate Shireto (average addition mole number of ethylene oxide =
15)

[0035]

[Table 2] Table 2: (b) Composition of nonionic base particles Sample No. Aioio component (wt%) AE * ¹ 15 30 − 15 60 FEE * ² − − 30 15 − Sodium carbonate 60 45 45 45 15 Zeolite (4A type) 20 20 20 20 20 Silica powder 2 2 2 2 2 Water Remainder Remainder Remainder Remainder * 1) AE: C ₁₂ Alcohol ethoxylate (average number of moles of ethylene oxide added = 8) * 2) FEE: C ₁₁ H ₂₃ CO (OCH ₂ CH ₂ ) ₁₅ OCH
₃

[0036]

[Table 3] Table 3: High bulk density granular detergent composition and its evaluation sample No. * ¹ 1 2 3 4 5 6 7 8 9 10 11 Composition (wt%) (a) Anion base particles A 80 80 80 80 80 − − − − − − B − − − − − 80 − − − − − C − − − − − − 80 − − − − D − − − − − − − 80 − − − − E − − − − − − − − 80 60 40 (b) Nonion-based particles A 19 − − − − − − − − − − A − 19 − − − 19 19 19 19 39 59 C − − 19 − − − − − − − − D − − − 19 − − − − − − − O − − − − 19 − − − − − − (c) Enzyme Protease * ² 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Lipase * ³ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 (a ') / (b') [wt ratio] 88/79/79/79/66/85/81/83/81/61/40 / 12 21 21 21 34 15 19 17 19 39 60 (a´) ＋ / (b´) [wt%] 25 27 27 27 33 37 31 35 30 30 30 Evaluation (remaining Activity:%) Protease 93 91 90 91 62 92 93 94 91 89 71 Lipase 88 87 85 85 56 87 89 90 88 82 63 * 1) Sample No. 5 and 11 are comparative examples, others are examples * 2) Novo enzyme, savinase 6.0T * 3) Novo enzyme, lipolase 100T

Claims (1)

[Claims] 1. (a) 5 to 40 anionic surfactant
(B) Nonionic surfactant containing 5 to 50% by weight of nonionic surfactant (c) Composed of a mixture with an enzyme and derived from anionic base particles of component (a) The weight ratio of (a ') anionic surfactant and (b') nonionic surfactant derived from the nonionic base particles of component (b) is (a ') / (b') = 9/1 to 5 / 5 and the total amount of (a ') and (b') is 5
A high bulk density granular detergent composition, characterized in that it is contained in an amount of ˜50% by weight.