JPH08157872A - Enzyme-containing liquid detergent composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition having high detergency for enzyme- sensitive stains, liquid stains and oil stains, by stably formulating a high- alkalinity liquid detergent for washing use with a combination of an enzyme with another desirable liquid detergent component. CONSTITUTION: This liquid detergent composition contains a surfactant, alkali protease enzyme and an enzyme stability system, with the weight ratio of the nonionic to anionic surfactants of 6 or higher, where pH of its stock liquor is >=9.5, and a solution pH after dilution is >=8.5, and the composition has an alkalinity capable of being titrated of >=0.5% per weight of the composition and water content of 15-60wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition containing an enzyme, more specifically,
The present invention relates to a liquid detergent composition for clothes containing an alkaline protease enzyme.

[0002]

2. Description of the Related Art In recent years, in spite of a remarkable improvement of an enzyme-stable system, the incorporation of an enzyme into a liquid detergent remains a difficult problem, and the problem of enzyme stability increases as the pH of the system increases. However, for the purpose of further improving the detergency against lipid stains and oil stains, there is a contradictory problem that high detergency cannot be obtained unless the pH of the system is increased.

[0003]

SUMMARY OF THE INVENTION The present invention provides a high pH laundry detergent with a stable blend of enzymes, which results in improved enzyme sensitivity and detergency against fatty and oily stains.

[0004]

SUMMARY OF THE INVENTION The inventors have discovered that a stable formulation of enzymes in a highly alkaline liquid laundry detergent in combination with other desirable liquid detergent ingredients. That is, the liquid detergent composition of the present invention is a liquid detergent composition containing a surfactant, an alkaline protease enzyme and an enzyme stabilizing system, and exhibits at least 35% of initial enzyme activity after storage at 40 ° C. for 2 weeks. So that (a)
The nonionic surfactant and the anionic surfactant are contained as the surfactant, and the ratio of the nonionic surfactant and the anionic surfactant is nonionic / anion = 6 or more by weight ratio, and (b) 9 It shows a stock solution pH of 0.5 or higher, and (c)
It has a solution pH of 8.5 or more when diluted at a rate of 0.2% in an aqueous washing liquid, and (d) when converted to a percentage of Na ₂ O and titrated to a pH of 7, the weight of the composition is It has a titratable alkalinity of at least 0.5% and is characterized by a water content of 15-60%.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The surfactant used in the liquid detergent composition of the present invention is used when the weight ratio of nonionic surfactant to anionic surfactant is nonionic / anion = 6 or more. Preferably non-ion / anion = 8-5
Used in the 0 range. If the ratio of the nonionic surfactant to the anionic surfactant deviates from this range, the cleaning performance for oil stains is deteriorated and the stability of the enzyme is deteriorated, which is not preferable.

The nonionic surfactant is not particularly limited as long as it is stable in the high pH detergent composition, but the following are preferable.

1) Polyoxyalkylene alkyl or alkenyl ether obtained by adding 6 to 18 mol of ethylene oxide (EO) and / or propylene oxide (PO) on average to a primary or secondary alcohol having 8 to 18 carbon atoms, 2) average A polyoxyethylene alkylphenyl ether having an alkyl group having 6 to 12 carbon atoms and added with an average of 6 to 20 mol of ethylene oxide,

3) an alkylamine oxide having an alkyl group or an alkenyl group having 10 to 20 carbon atoms, 4) a product obtained by adding ethylene oxide to a condensate of propylene oxide and propylene glycol (a pluronic type surfactant),

5) A product obtained by adding ethylene oxide to a condensate of propylene oxide and ethylenediamine (tetronic type surfactant), and these alkyl groups or alkenyl groups may be linear or branched. Of these, more preferred are polyoxyethylene polyoxypropylene alkyl ethers among the nonionic surfactants of 1) above.

Examples of the anionic surfactant include alkylbenzene sulfonate, higher fatty acid salt, polyoxyalkylene alkyl sulfate ester salt, alkyl sulfate ester salt, and α-olefin sulfonate. The total amount of these surfactants is not particularly limited, but is preferably 20% by weight or more, more preferably 3%.
It is used in the range of 0% to 70% by weight.

Alkaline protease enzymes used in the present invention include "Savinase" and "Alcalase (Alcalase) manufactured by Novo Industries.
, ”,“ Esperase ”,
Examples include "Durazyme", "Maxapem" manufactured by Gist Brokers, "Maxatase", and "Bioprase" manufactured by Nagase Seikagaku Co., Ltd., which are used alone. Alternatively, two or more kinds may be used in combination.

The blending amount of these enzymes is not particularly limited, but is preferably 0.1% by weight to 3% by weight, more preferably 0.3% by weight to 2% by weight.

The liquid detergent composition of the present invention has a pH of undiluted solution.
Of 9.5 or more, preferably 10 or more, and a washing liquid p of 8.5 or more when diluted at a rate of 0.2% in an aqueous washing liquid.
It is necessary to indicate H. Further, when converted to Na ₂ O content and titrated up to pH 7, it is necessary to have a titratable alkalinity of at least 0.5% based on the weight of the composition. Examples of the alkali agent for adjusting the alkalinity of the present invention include alkali metal hydroxides, silicates, carbonates and alkanolamines, with alkanolamines being preferred.

In the present invention, it is desirable to add an enzyme stabilizing system (agent), and it is preferable to add a polyol, a boron compound, a calcium ion, and a polyfunctional amino compound individually or in combination. As the polyol, ethylene glycol, propylene glycol, dipropylene glycol, glycerol or the like is used.

Examples of the boron compound include boron oxide, boric acid and alkali metal borate. Calcium ions are incorporated in the form of water-soluble salts such as calcium chloride. Examples of polyfunctional amino compounds include diethanolamine and triethanolamine. The liquid detergent composition of the present invention has a water content of 15 to 60% by weight and is preferably prepared in the form of an isotropic liquid.

Further, in the liquid detergent composition of the present invention, various additives usually used in detergent compositions, for example, hydrotropes such as lower alcohols, polyhydric alcohols and lower aryl sulfonates, Benzoates, preservatives such as isothiazolone compounds, rinse improvers such as silicones, accidental ingestion agents such as bitterness / emetics, optical brighteners, dyes, fragrances, antioxidants, etc. may be added as necessary. it can.

[0017]

Industrial Applicability According to the present invention, it is possible to stably mix an enzyme with other desirable liquid detergent components in a liquid detergent for laundry having high alkalinity, and to remove enzyme-sensitive stains and fats. It is possible to realize a liquid detergent composition exhibiting high cleaning performance against both quality stains and oil stains.

[0018]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

<< Testing Method for Detergency >> US. Testing
Terg-O-Tometer of the same company was used as a cleaning device, and a commercially available contaminated cloth No. No. of EMPA of Switzerland was used as an oil stain. 101 cut into 5 cm x 5 cm 10
A sheet, a sebum cloth, and a clean knitted cloth are put therein, and the bath ratio is adjusted to 30 times, followed by washing at 120 rpm and 25 ° C. for 10 minutes. As the cleaning liquid, 900 mL of a cleaning agent concentration of 0.10% is used, and rinsing is performed with 900 mL of water for 3 minutes. Water used is 3 degrees DH
I used the one. The detergency was calculated by the following formula 1.

[0020]

[Equation 1] K / S = (1-R / 100) ² / (2R / 100) R is reflectance (%)

<Enzyme Stability Evaluation Method> Enzyme stability was determined by placing 100 mL of the detergent composition under test in a glass bottle and storing the composition at 40 ° C. for 2 weeks. Expressed as a fraction. ◯: 35% or more remained ×: Residual ratio less than 35%

<< Evaluation Method for Alkalinity >> Various liquid detergent compositions were prepared and their alkalinity was measured, and the results are shown in the table. The alkalinity is 0.
5 g was collected and calculated by titrating to pH 7 with 0.1 N hydrochloric acid. ◯: Alkalinity of 0.5% or more ×: Alkalinity of less than 0.5%

<< pH Measuring Method >> Various liquid detergent compositions were prepared and their pHs were measured using a pH meter. The results are shown in the table. (A) Undiluted solution pH ⊚: pH = 10 or more ◯: pH = 9.5 or more and less than 10 ×: pH = 9.5 or less (b) pH at 0.2% dilution ◯: pH = 8.5 or more ×: pH = Less than 8.5 Examples / Comparative Examples 1 to 13 Various liquid detergent compositions having the compositions shown in Table 1, Table 2 and Table 3 were prepared and evaluated, and the results are shown in the same table.

[0024]

[Table 1]Table 1: Composition, properties and evaluation results Example 1 2 3 4 5 Composition (wt%) Palm alcohol (EO)₉(PO)₂H 50 50 − 10 45 Diadol 13 (EO)₁₂(PO)₂H *¹− − 50 40 − Diethanolamine oleate 2 5 − 2 1 LAS *²− − 5 − − Diethanolamine 15 15 15 15 15 MAXAPEM L30 0.6 0.5 − 0.9 0.6 DURASYM 16.0L − − 0.6 − − Ethanol 8 8 8 8 8 Borax pentahydrate − − 1.0 − − Calcium chloride 0.01 0.01 0.01 0.02 0.02 Water 22.39 21.49 20.39 24.08 30.38 Undiluted solution pH ◎ ◎ ◎ ◎ ◎ ◎ 0.2% diluted pH ○ ○ ○ ○ ○ Alkalinity ○ ○ ○ ○ ○ Non-ion / anion ratio 25 10 10 25 45 Detergency 47 45 47 46 45 Enzyme stability ○ ○ ○ ○ ○ * 1) Polyoxyethylene polyoxypropylene alkyl ether in which 12 mol of ethylene oxide and 2 mol of propylene oxide are added to Diadol 13 on average. Diadol 13 is a branched higher synthetic alcohol having a carbon number of 13 as a main component (linear rate 60%) (manufactured by Mitsubishi Chemical Corporation) * 2) linear alkyl (C₁₁~ C₁₃) Benzenesulfonic acid diethanolamine

[0025]

[Table 2]Table 2: Composition, properties and evaluation results Example Comparative example 6 7 8 9 10 Composition (wt%) Palm alcohol (EO)₉(PO)₂H 50 50 30 50 50 Diadol 13 (EO)₁₂(PO)₂H *¹− − − − − Diethanolamine oleate − 2 − 12 LAS *²1.5 − 20 − − Diethanolamine 15 15 15 15 − MAXAPEM L30 − 0.6 0.6 0.6 0.6 DURASYM 16.0L 0.6 − − − − Ethanol 8 8 8 8 8 Borax pentahydrate − − − − − Calcium chloride 0.02 0.01 0.01 − 0.01 Water 24.88 24.39 26.39 25.4 39.39 Undiluted solution pH ◎ ◎ ◎ ◎ × 0.2% diluted pH ○ ○ ○ ○ × Alkalinity ○ ○ ○ ○ × Non-ion / anion ratio 33 25 1.5 50 25 Detergency 47 45 35 47 25 Enzyme stability ○ ○ × × ○ * 1) Polyoxyethylene polyoxypropylene alkyl ether obtained by adding 12 mol of ethylene oxide and 2 mol of propylene oxide on average to Diadol 13 * 2) Linear alkyl (C₁₁~ C₁₃) Benzenesulfonic acid diethanolamine

[0026]

[Table 3] Table 3: Composition, properties and evaluation results Example 11 12 13 Composition (wt%) Palm alcohol (EO) ₃ (PO) ₂ H * ¹ 50 50 50 Oleic acid diethanolamine 2 2 2 Diethanolamine 15 15 15 Alcalase 8.0L 0.9 − − Savinase 16L − 0.5 − Maxatase LS − − 0.5 Ethanol 8 8 8 Borax pentahydrate 1.0 − − Calcium chloride 0.01 0.01 0.01 Water 23.09 24.49 24.49 Undiluted solution pH ◎ ◎ ◎ 0.2% diluted pH ○ ○ ○ Alkalinity ○ ○ ○ Non-ion / anion ratio 25 25 25 Detergency 47 47 47 Enzyme stability ○ ○ ○ * 1) Polyoxyethylene poly obtained by adding 3 mol of ethylene oxide on average and 2 mol of propylene oxide on average to palm alcohol. Oxypropylene alkyl ether

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[Procedure amendment]

[Submission date] March 20, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

[0026]

[Table 3] Table 3: Composition, properties and evaluation results Example 11 12 13 Composition (wt%) Palm alcohol (EO) ₉ (PO) ₂ H * ¹ 50 50 50 Diethanolamine oleate 2 2 2 Diethanolamine 15 15 15 Alcalase 8.0L 0.9 − − Savinase 16L − 0.5 − Maxatase LS − − 0.5 Ethanol 8 8 8 Borax pentahydrate 1.0 − − Calcium chloride 0.01 0.01 0.01 Water 23.09 24.49 24.49 Undiluted solution pH ◎ ◎ ◎ 0.2% diluted pH ○ ○ ○ Alkalinity ○ ○ ○ Non-ion / anion ratio 25 25 25 Detergency 47 47 47 Enzyme stability ○ ○ ○ * 1) Polyoxyethylene poly obtained by adding 9 mol of ethylene oxide on average and 2 mol of propylene oxide on average to coconut alcohol. Oxypropylene alkyl ether

Claims (5)

[Claims] 1. A liquid detergent composition containing a surfactant, an alkaline protease enzyme and an enzyme stabilizing system,
Initial enzyme activity of at least 35 after storage for 2 weeks at 40 ° C
%, (A) contains a nonionic surfactant and an anionic surfactant as the surfactant, and the ratio of the nonionic surfactant to the anionic surfactant is nonionic / anion = 6 by weight ratio. Above, (b) shows a pH of the stock solution of 9.5 or more, and (c) when diluted in an aqueous washing solution at a ratio of 0.2%.
It has a solution pH of 5 or more, and (d) has a titratable alkalinity of at least 0.5% based on the weight of the composition when converted as a% of Na ₂ O and titrated to pH 7. Water content is 15-60%
A liquid detergent composition comprising: 2. The liquid detergent composition according to claim 1, wherein the nonionic surfactant is polyoxyethylene polyoxypropylene alkyl ether. 3. The liquid detergent composition according to claim 1, wherein the pH of the undiluted solution is 10 or more. 4. The method according to claim 1, which is in the form of an isotropic liquid.
The liquid detergent composition according to claim 1. 5. The alkaline protease is Alcalas.
e ™, Savinase ™, Durasy
m (trademark), Maxatase (trademark), Maxape
The liquid detergent composition according to any one of claims 1 to 4, which is selected from the group consisting of m (trademark).