Liquid detergent composition and washing method

Abstract

To provide a composition exhibiting high proteolytic power and high detergency.SOLUTION: There are provided a liquid detergent composition for clothing containing a protease having all of the following three characteristics and a nonionic surfactant, and a washing method using the same: (1) An activity value at pH 12.0 is 85% or more of an activity value at an optimum pH; (2) The enzyme titer at the addition of 0.2 mass% of EDTA-4Na is 90% or more of that without EDTA-4Na; (3) The optimum temperature is 60°C or higher.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid detergent composition and a washing method having a high detergency including protein stain removal power even when washed at a high temperature of 60 ° C or higher.

Background Art

[0002] Especially in commercial laundering, when washing clothes with complex adhesion of sebum stains, protein stains, particulate stains, etc., such as shirts and uniforms worn for a long time, kitchen white clothes, work clothes in a machine factory, etc., the stains cannot be sufficiently removed by washing at room temperature, and high-temperature washing at 60 ° C or higher using a surfactant (liquid detergent or powder detergent) and an alkaline agent is performed.

[0003] However, when these clothes are directly washed at a high temperature of 60 ° C or higher, the protein stains become difficult to remove because they are denatured and solidified by heat before being removed. Therefore, first, the temperature is once set to room temperature to 40 ° C so as not to solidify the protein stains, and the clothes are washed in an alkaline bath, and then the washing temperature is raised to 60 ° C or higher to remove other stains. A two-step washing process was required.

[0004] However, even when the two-step washing is performed, the removal of protein stains may be insufficient, or the attached protein stains may have already deteriorated due to heat or over time. Therefore, a detergent containing protease, which is a protein-degrading enzyme, is often used. However, in washing at 60 ° C or higher, there is a problem that protease does not act effectively and cannot sufficiently remove stains.

[0005] In addition, a method of applying a surfactant or an enzyme preparation to the stained part in advance and then washing after leaving it may be considered. However, in commercial laundering where a large number of items to be washed need to be processed at once, such a method of applying one by one greatly reduces productivity and is inefficient. Thus, there has been a demand for a cleaning agent that can be used in cleaning at a high temperature of 60°C or higher and has a high ability to remove protein stains, without adopting time-consuming methods such as two-step cleaning or cleaning after applying and leaving a cleaning component.

[0006] For example, Patent Document 1 reports a liquid detergent composition containing (a) 5 to 40% by mass of a nonionic surfactant represented by [R-O-(EO) n -H] (where R is an alkyl or alkenyl group having 10 to 20 carbon atoms, EO is ethylene oxide, and n is the average number of moles of ethylene oxide added, with an average added mole number of ethylene oxide of 2 to 10), (b) 0.1 to 2.0% by mass of a saturated fatty acid having 14 to 18 carbon atoms or a salt thereof in terms of saturated fatty acid, (c) a protease preparation, and (d) a citrate, and substantially not containing an anionic surfactant other than the fatty acid salt derived from component b. Patent Document 1 examines low foaming properties during cleaning, rinsing properties, sebum stain removal cleaning power at 25°C, and transparent and uniform appearance stability.

[0007] Patent Document 2 reports a liquid detergent composition containing (a) 10 to 50% by mass of a nonionic surfactant containing 6 to 15% by mass of a compound represented by the formula R-O(AO) n -H [wherein R is a hydrocarbon group having 8 to 22 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is a number selected from 0, 1, and 2], (b) 0.5 to 10% by mass of a fatty acid having an average carbon number of 8 to 20, (c) 0.5 to 5% by mass of a chelating agent, (d) an enzyme containing protease, and (e) an enzyme stabilizer. Patent Document 2 examines the stability of the enzyme and the detergency of socks at 20°C.

[0008] Patent Document 3 reports a composition containing (A) a nonionic surfactant, (B) an anionic surfactant, (C) a protease, and (D) an alkylene terephthalate unit and an alkylene isophthalate unit A water-soluble polymer having at least one unit selected from the group consisting of units and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units, and (E) at least one component selected from the group consisting of α-hydroxy-monocarboxylic acids and salts thereof, wherein the total content of all surfactants is 45% by mass or more based on the total mass of the liquid detergent, and the content of the component (B) is 4% by mass or more based on the total mass of the liquid detergent. A liquid detergent has been reported. In Patent Document 3, the stability and appearance stability of enzymes under high concentrations of surfactants are examined.

[0009] Patent Document 4 reports a liquid detergent composition for clothing, which contains (A) 36 to 70% by mass of a nonionic surfactant composed of (A-1) an ethylene oxide adduct of an alcohol having a monovalent hydrocarbon group with 12 carbon atoms, with an average addition of 10 to 20 moles of ethylene oxide, and (A-2) an ethylene oxide adduct of an alcohol having a monovalent hydrocarbon group with 13 or 14 carbon atoms, with an average addition of 10 to 20 moles of ethylene oxide, and the mass ratio thereof being (A-1) / (A-2) = 0.1 to 4, (B) 0.1 to 2% by mass of protease, and (C) 0.0001 to 0.01% by mass of calcium chloride. In Patent Document 4, the stability of the enzyme and the detergency of sebum stains at 20°C are examined.

[0010] Patent Document 5 reports a liquid detergent composition for clothing, which contains (a) 10 to 30% by mass of R-O-(EO) n -H (wherein R is an alkyl group or alkenyl group having 10 to 20 carbon atoms, EO is an oxyethylene group, n is the average number of added moles, and is a numerical value in the range of 8 to 26), (b) 0.05 to 1.0% by mass of protease enzyme, (c) an antibacterial solvent, and (d) a crosslinked carboxyvinyl polymer, and the liquid viscosity at a liquid temperature of 10 to 30°C is 50 to 1,000 mPa·s. In Patent Document 5, the stability of the enzyme, the viscosity of the composition, and the detergency of sebum stains at 25°C are examined.

[0011] Patent Document 6 reports a liquid detergent composition characterized by containing: Component (A): a surfactant containing 60% by mass or more of a nonionic surfactant in Component (A); Component (B): a homopolyamino acid and / or its salt; Component (C): an enzyme containing protease; and Component (D): water. Patent Document 6 examines the stability of the enzyme and the detergency of sebum stains at 20°C.

[0012] Patent Document 7 discloses that component (a) is R 1 (CO) m O-(A 1 O) n -R 2 〔In the formula, R 1 is a primary aliphatic hydrocarbon group having 9 to 16 carbon atoms, R 2 is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, the A 1 O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is the average number of added moles, which is a number of 2 or more and 30 or less.〕 A nonionic surfactant represented by; component (b) is a polyoxyethylene alkyl ether sulfate; component (c) is (M x+ ) y SO 4 2- (c1)〔In the formula, (M x+ ) is one or more ions selected from a sodium ion, a potassium ion, a magnesium ion, an ammonium ion, and an alkanolammonium ion having 2 to 6 carbon atoms. x is the valence of the ion, which is a number of 1 or 2. When x is 1, y is a number of 2, and when x is 2, y is a number of 1.〕; component (d) is protease, contains water, the content of component (a) is 5% by mass or more and 30% by mass or less, the mass ratio of the content of component (a) to the content of component (b) is 0 or more and 0.45 or less in 〔(content of component (b))〕 / 〔(content of component (a))〕, and the content of component (c) is 0.5% by mass or more and 4% by mass or less. A liquid detergent composition for clothing has been reported. Patent Document 7 examines the stability of the enzyme and the detergency of protein stains at 20°C.

[0013] Patent Document 8 discloses that component (a) is an alkyl sulfate salt having 10 to 18 carbon atoms; component (b) is R-O-(AO) n -SO 3 M [wherein, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, n is an integer of 1 or more and 20 or less, and M is a cation.]; component (c) is a nonionic surfactant; component (d) is one or more sulfates selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate); component (e) is a protease containing water, the total content of component (a) and component (b) is 5% by mass or more and 40% by mass or less, the content of component (d) is 2% by mass or more and 8% by mass or less, and the mass ratio of the content of component (a) to the content of component (b) is 0.5 or more and 10 or less as [content of component (a)] / [content of component (b)], and a liquid detergent composition for clothing has been reported. Patent Document 8 examines the stability of the enzyme and the detergency of protein stains at 30°C.

[0014] All of the detergent compositions disclosed in Patent Documents 1 to 8 report compositions containing a protease and a nonionic surfactant, but their detergency has only been examined at temperatures of about 20 to 30°C. As a result of investigations by the present inventors, the ability to remove protein stains in washing at high temperatures of 60°C or higher shown by the compositions reported in Patent Documents 1 to 8 was not sufficient.

[0015] Patent Document 9 reports that Esperase (registered trademark) is a protease suitable for washing at high temperatures. However, nothing is shown regarding the chelate stability and the optimum temperature of Esperase (registered trademark).

Prior Art Documents

Patent Documents

[0016]

Patent Document 1

[0017] An object of the present invention is to provide a detergent composition that exhibits high proteolytic activity and high detergency at a high temperature of 60°C or higher. [Means for Solving the Problems]

[0018] The present inventor has found that such problems can be solved by using a liquid laundry detergent composition containing a protease having specific characteristics and a nonionic surfactant, and has completed the present invention. That is, the present invention is characterized by the following points.

[0019] 1. (1) The activity value at pH 12.0 is 85% or more of the activity value at the optimum pH; (2) The activity value when 0.2% by mass of EDTA-4Na is added is 90% or more of the activity value when no EDTA-4Na is added; (3) A liquid laundry detergent composition containing a protease (excluding Esperase (registered trademark)) having all three characteristics of an optimum temperature of 60°C or higher and a nonionic surfactant. 2. Further, a liquid detergent composition for clothing, which contains a fatty acid or a fatty acid salt. 3. Further, a liquid detergent composition for clothing, which contains a chelating agent. 4. A washing method for washing clothes using the liquid detergent composition for clothing according to any one of 1 to 3 above. 5. A washing method in which the washing is performed at a temperature of 55°C or higher and under alkaline conditions. 6. A washing method in which the washing is performed at a temperature of 60 to 80°C. 7. The washing method according to 5 or 6 above, in which the washing is performed under the condition of pH 9 to 13. Here, the activity value refers to the protein degradation ability of an enzyme (protease) under certain conditions (pH, temperature, time, etc.).

Effects of the Invention

[0020] According to the present invention, it is possible to provide a composition that exhibits high protein degradation power and high detergency at a high temperature of 60°C or higher.

Modes for Carrying Out the Invention

[0021] Hereinafter, the present invention will be described in detail. The composition of the present invention contains a protease having all of the following three characteristics: (1) the activity value at pH 12.0 is 85% or more of the activity value at the optimum pH, (2) the activity value when 0.2% by mass of EDTA-4Na is added is 90% or more of the activity value when no EDTA-4Na is added, and (3) the optimum temperature is 60°C or higher, and a nonionic surfactant. Protease is a general term for peptide bond hydrolases and is widely used in detergent compositions. The protease used in the present invention needs to satisfy all of the three characteristics described below.

[0022] The determination methods for the three characteristics satisfied by the protease contained in the composition of the present invention will be described in order. (1) The activity value at pH 12.0 is 85% or more of the activity value at the optimum pH (optimum pH) The protease contained in the composition of the present invention exhibits maintenance of 85 to 100% activity even when used at pH 12.0 as compared to the activity at the optimum pH. This index designates the pH at which protease activity is highest when milk casein is used as the substrate as the optimum pH, and defines that "the activity value at pH = 12.0 is 85% or more of the activity value at the optimum pH" when the activity value of the protease at pH = 12.0 is 85% or more of the activity value at the optimum pH. (2) The activity value when 0.2% by mass of EDTA-4Na is added is 90% or more of the activity value when no EDTA-4Na is added (chelate resistance stability) The protease contained in the composition of the present invention has high chelate resistance stability. This index measures the activity value when EDTA-4Na is added to a solution containing 0.01% by mass of protease to a concentration of 0.2% by mass and the mixture is held at pH = 7.5 for 30 minutes at 40°C, and defines that "the activity value when 0.2% of EDTA-4Na is added is 90% or more of the activity value when no EDTA-4Na is added" if this value is 90% or more of the activity value when no EDTA-4Na is added. (3) Optimum temperature of 60°C or higher (optimum temperature) The protease contained in the composition of the present invention exhibits high activity at temperatures of 60°C or higher. This index designates "optimum temperature of 60°C or higher" when the temperature at which protease activity is highest when measuring protease activity at pH = 10.0 using milk casein as the substrate at each temperature is 60°C or higher. Note that the proportion of protease in the composition is appropriately adjusted, but from the viewpoint of detergency, it is preferably 0.005 to 20% by mass. More preferably, it is 0.5 to 15% by mass, and even more preferably, it is 2 to 10% by mass.

[0023] Next, regarding the nonionic surfactant, which is another component of the composition of the present invention, as long as the dirt can be removed, the type thereof is not particularly limited. However, from the viewpoint of the detergency of cotton products, nonionic surfactants that are alkylene oxide adducts of higher alcohols and alkylene oxide adducts of alkylamines are desirable. From the viewpoint of the detergency of PET products, nonionic surfactants that are alkylene oxide adducts of mono- or / and di- or / and tristyrenated phenols are preferred. These nonionic surfactants can be used alone or in combination. More preferably, an example can be given of a combination of an alkylene oxide adduct of a higher alcohol (which may be single or two or more kinds, and in the case of two or more kinds, the sum of the values obtained by multiplying each HLB value by its respective mass ratio should be 13 to 15) having a Griffin HLB value of 13 to 15 and an alkylene oxide adduct of distyrenated phenol. The proportion of the nonionic surfactant in the composition is adjusted as appropriate, but from the viewpoints of detergency, the viscosity of the composition, and the handleability of the composition, it is preferably 0.02 to 99% by mass, more preferably 10 to 70% by mass, and even more preferably 15 to 50% by mass.

[0024] In the present invention, both components are dissolved in water (such as ion-exchanged water, pure water, etc.) to form a liquid composition.

[0025] In the composition of the present invention, other components known to be formulated in detergent compositions in the technical field of detergents can be formulated within the range that does not affect the performance of the present invention. Examples of such components include, but are not limited to, fatty acids, fatty acid salts, chelating agents, stabilizers, anionic surfactants, water-miscible organic solvents, thickeners, thinning agents, solubilizers, alkali agents, other chelating agents, antioxidants, preservatives, other enzymes, fragrances, colorants, emulsifying agents, natural products, pH adjusters, antifoaming agents, texture improvers, storage stability improvers, fluorescent agents, migration inhibitors, recontamination inhibitors, pearlescent agents.

[0026] Fatty acids and fatty acid salts mainly function as defoaming agents. Examples of such fatty acids and fatty acid salts include fatty acids (salts) having 12 to 18 carbon atoms. Specifically, coconut fatty acid (salt), stearic acid (salt), etc. can be exemplified. It can be blended in an amount of 0.01 to 10% by mass based on the composition. The chelating agent has a function of stabilizing each component in the composition. Examples of such chelating agents include organic chelating agents. Specifically, aminocarboxylic acid-based chelating agents (for example, EDTA, NTA, DTPA, MGDA, GLDA, HEIDA, etc.) can be used. The ratio of the chelating agent in the composition is appropriately adjusted, but from the viewpoints of defoaming property and stability of the composition, it can be blended in an amount of 0.5 to 10% by mass based on the blending amount of the enzyme raw material of the composition. As the stabilizer, various ones can be used and there is no particular limitation, but glycol-based solvents such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, benzyl alcohol, 3-methyl-3-methoxy-butanol, etc. can be exemplified. The blending amount in the composition can be appropriately determined according to the purpose of use within a range that does not interfere with the detergency of the composition of the present invention.

[0027] Next, the washing method will be described. The washing using the composition of the present invention is suitable for so-called clothing washing. Specific washing methods include methods of applying physical external forces such as stirring, rotation, dropping, vibration, etc. for washing. As a specific example, using the composition of the present invention, clothing can be washed using an industrial automatic washing machine, a continuous washing machine, or a household washing machine. The amount of the cleaning agent composition of the present invention used in cleaning is not particularly limited and is appropriately determined during cleaning. From the viewpoints of detergency and defoaming property, it is preferable to formulate the composition of the present invention so that the protease in the cleaning liquid or the cleaning agent composition is 0.001 to 10% by mass, or the nonionic surfactant is 0.001 to 5% by mass.

[0028] The cleaning temperature is not particularly limited and is appropriately determined during cleaning. However, in order to most effectively bring out the desired effects of the composition of the present invention, it is preferable to carry out cleaning at 55 to 85°C. A more preferable cleaning temperature is 60 to 80°C, and an even more preferable cleaning temperature is 70 to 80°C. The cleaning time is not particularly limited and is appropriately determined during cleaning. However, from the viewpoint of detergency, it is preferably 1 to 60 minutes. More preferably, it is 3 to 30 minutes, and even more preferably, it is 5 to 20 minutes.

[0029] The pH of the cleaning liquid is preferably 8 or higher. From the viewpoints of detergency and prevention of embrittlement of the object to be cleaned, such as clothing, it is more preferably pH 9 to 13, and even more preferably pH 10 to 12. The method for adjusting the pH of the cleaning liquid is not particularly limited, but sodium orthosilicate, sodium metasilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, potassium orthosilicate, potassium metasilicate, potassium silicate No. 1, potassium silicate No. 2, potassium silicate No. 2, caustic soda, caustic potash, sodium carbonate, potassium carbonate, alkanolamines, sodium tripolyphosphate, etc. can be used.

[0030] In the case of washing, within the range that does not interfere with the detergency of the composition of the present invention, for example, liquid detergents, powder detergents; various surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants; inorganic compounds such as silicates, carbonates, sulfates; chelate compounds such as tripolyphosphates and aminocarboxylates; bleaching agents such as hydrogen peroxide and sodium hypochlorite; organic solvents such as alcohol-based solvents, glycol-based solvents, hydrocarbon-based solvents; enzymes such as other proteases, lipases, amylases, cellulases; antioxidants, preservatives, fragrances, colorants, emulsifiers, antibacterial agents, natural products, pH adjusters, defoamers, texture improvers, storage stability improvers, fluorescent agents, anti-migration agents, anti-redeposition agents, soil release agents, pearl agents, etc. may be used. These blending amounts can be appropriately determined according to the purpose of use within the range that does not interfere with the detergency of the composition of the present invention.

[0031] Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.

Examples

[0032] [Selection of Protease] As proteases, Progress UNO 100L, Esperase 8.0L, Savinase 16L, Alcalase 2.5L (all above, manufactured by NOVO), Clinase SAP-200L, Clinase CAP-200L, Clinase AP-200L (all above, manufactured by Nippon Koyken), Bioprase APL-30, Bioprase 30L (all above, manufactured by Nagase ChemteX), EFFECTENZ P150, PREFERENZ P300 (all above, manufactured by DuPont) were used, and according to the following method, it was determined whether each protease satisfied the requirements of the present invention, namely, (1) the activity value at pH 12.0 was 85% or more of the activity value at the optimum pH <optimum pH>, (2) the activity value when 0.2% by mass of EDTA-4Na was added was 90% or more of the activity value when EDTA-4Na was not added <chelating stability>, (3) the optimum temperature was 60°C or higher <optimum temperature>.

[0033] <(1) Optimum pH> Using 100 mM of sodium phosphate buffer (pH 6.0 - 8.0), Tris - hydrochloric acid buffer (pH 8.0 - 9.0), glycine - sodium hydroxide buffer (pH 9.0 - 10.0), boric acid - sodium hydroxide buffer (10.0 - 11.0) or sodium phosphate - sodium hydroxide buffer (pH 11.0 - 12.0), various solutions with different pH values containing 0.6% by mass of milk casein as a substrate were prepared. For the others, protease activities were measured under various pH conditions according to the following method for measuring enzyme titer. The pH condition with the highest protease activity was defined as the optimal pH of the protease. Also, the protease activity value at pH 12 was calculated as a percentage of the protease activity value under the optimal pH condition. As a result, those with 85% or more were evaluated as ○, and the others were evaluated as ×.

[0034] <(2) Chelating resistance stability> To the enzyme raw material solution diluted to 0.01% with a diluent (3 g / l of sodium chloride, 0.175 g / l of calcium acetate, 1.667 g / l of sodium acetate, (pH 7.5)), EDTA - 4Na was added to a concentration of 0.2% by mass, and after holding at 40 °C for 30 minutes at pH 7.5, the remaining protease activity was measured according to the following method for measuring enzyme titer. Similarly, the protease activity value in the case without addition of EDTA - 4Na was measured, and the ratio of the protease activity when EDTA - 4Na was added to that without addition of EDTA - 4Na was calculated. As a result, those with 90% or more were evaluated as ○, and the others were evaluated as ×.

[0035] <(3) Optimal temperature> Using a 0.6% by mass solution of milk casein adjusted to pH = 10.0 with boric acid - sodium hydroxide buffer, according to the following method for measuring enzyme titer, the protease activity when reacted for 10 minutes at each temperature was determined, and the temperature with the highest activity value was defined as the optimal temperature. Those with an optimal temperature of 60 °C or higher were evaluated as ○, and the others were evaluated as ×.

[0036] <Enzyme titer> To 5 ml of the reaction solution (0.6% by mass of milk casein (manufactured by Merck & Co., Inc.), 0.55% by mass of disodium hydrogen phosphate (pH 7.5)), add 1 ml of the enzyme raw material solution diluted to 0.01% by mass with the dilution solution (3 g / l of sodium chloride, 0.175 g / l of calcium acetate, 1.667 g / l of sodium acetate, (pH 7.5)), and react at 30°C for 10 minutes. After the reaction, add 5 ml of trichloroacetic acid solution (17.97 g / l of trichloroacetic acid, 18.04 g / l of anhydrous sodium acetate, 19.81 g / l of acetic acid), leave it at 30°C for 30 minutes, and then filter with a membrane filter (0.45 μm). To 2 ml of the filtrate, add 5 ml of 0.55 M sodium carbonate and 1 ml of Folin reagent (Folin reagent: ion-exchanged water = 1:2), leave it at 30°C for 30 minutes, and then measure the absorbance (660 nm). Based on the Folin chromogenicity (absorbance) exhibited by L-tyrosine, the enzyme activity that gives an absorbance equivalent to the absorbance exhibited by 1 μg of L-tyrosine in the entire reaction solution per minute at 30°C was defined as 1 protease unit (1 PU), and the enzyme titer was calculated.

[0037] Note that the activity value of the "protease activity" mentioned here represents the protein degradation ability of the enzyme (protease) under certain conditions (pH, temperature, time, etc.), and the enzyme titer is a unit indicating the activity value of the enzyme, expressed in PU / ml. The results are shown in Table 1.

[0038]

Table 1

[0039] As shown in Table 1, among the 11 types of proteases used in the experiment, only two types, Progress UNO 100L and Esperase 8.0L, were confirmed to satisfy the following conditions: (1) the activity value at pH 12.0 is 85% or more of the activity value at the optimum pH, (2) the activity value when 0.2% of EDTA-4Na is added is 90% or more of the activity value without the addition of EDTA-4Na, and (3) the optimum temperature is 60°C or higher. The others do not satisfy at least one of the requirements (1) to (3).

[0040] [Adjustment of Composition] The composition was adjusted with the composition (mass %) described in Table 2. Each component used is as follows. <Nonionic surfactant> · C12 alcohol EO9: Softanol 90 manufactured by Nippon Catalyst · C12 alcohol EO12: Softanol 120 manufactured by Nippon Catalyst · C12 alcohol EO15: Softanol 150 manufactured by Nippon Catalyst · C12 alcohol (EO1 / PO2)(EO3 / PO1): manufactured by Nikka Chemical · C12 alcohol EO3(EO1.5 / PO2.5)EO1.5: manufactured by Nikka Chemical · C12 alcohol EO3(EO2.5 / PO2.5)EO3: manufactured by Nikka Chemical · C12 alcohol EO3(EO3 / PO2.5)EO8: manufactured by Nikka Chemical · Distyrenated phenol EO12: manufactured by Nikka Chemical · C18 amine EO20: manufactured by Nikka Chemical Note that EO represents an ethyleneoxy group, PO represents a propyleneoxy group, and the numbers represent the number of added moles. For example, C12 alcohol (EO1 / PO2)(EO3 / PO1) represents a structure in which 1 mole of EO and 2 moles of PO are randomly added to an alcohol having 12 carbon atoms, and then 3 moles of EO and 1 mole of PO are randomly added. C12 alcohol EO3(EO1.5 / PO2.5)EO1.5 represents a structure in which 3 moles of EO are added to an alcohol having 12 carbon atoms, then 1.5 moles of EO and 2.5 moles of PO are randomly added, and finally 1.5 moles of EO are added.

[0041] <Chelating agent> · NTA-3Na (sodium nitrilotriacetate): Kurewate P manufactured by Nagase ChemteX C-C3 · EDTA-4Na (tetrasodium ethylenediaminetetraacetate): Kurewate S2 manufactured by Nagase ChemteX · DTPA-5Na (pentasodium diethylenetriaminepentaacetate): Kurewate DP-80 manufactured by Nagase ChemteX <Fatty acid> · Coconut fatty acid: Coconut soap made by Nippon Oil & Fats Co., Ltd. · Stearic acid: Stearic acid 300 made by Shin Nippon Rika Co., Ltd. <Neutralizing agent> · Sodium hydroxide: Liquid caustic soda made by Tokuyama Corporation

[0042] [Washing method] As the washing device, a Tergotometer (manufactured by Daiei Scientific Instruments Co., Ltd.) was used. As the objects to be washed, wet artificially contaminated cloth (manufactured by the Laundry Science Association, Inc.) and EMPA116 contaminated cloth (manufactured by the Swiss Federal Laboratories for Materials Testing and Research) were used. Four pieces each of the above wet artificially contaminated cloth and the above EMPA116 contaminated cloth cut into 4 × 5 cm were washed with 500 ml of various solutions in Examples 1 to 30 and Comparative Examples 1 to 6. The washing temperature was 60 °C, or 70 °C, or 80 °C, the washing time was 15 minutes, and the rotation speed was 90 rpm.

[0043] [Evaluation] <Appearance stability> The prepared composition was put into a 200 ml mayonnaise bottle and left standing in a constant temperature bath at 45 °C, 25 °C, and -5 °C for 1 week each. After 1 week, the appearance was visually inspected, and those without sediment or precipitate were rated as ○. <ph> The pH of the composition immediately after preparation was measured using a pH meter.

[0044] <Washing rate> After washing, the above-mentioned wet artificially contaminated cloth and EMPA116 contaminated cloth were rinsed and dried, and the reflectance (550 nm) of the surface of the contaminated cloth was measured using a colorimeter CM-53D (manufactured by Murakami Color Technology Research Institute), and the washing rate was calculated using the following formula. Washing rate (%) = 100 × [(reflectance after washing - reflectance before washing) / (reflectance of white cloth - reflectance before washing)] The evaluation of the wet artificially contaminated cloth was carried out at washing temperatures of 60 °C and 70 °C. Regarding the washing rate of the wet artificially contaminated cloth, when the average value of the washing rates of 4 contaminated cloths was less than 45%, it was rated as ×; when it was 45% or more and less than 50%, it was rated as △; when it was 50% or more and less than 55%, it was rated as ○; when it was 55% or more, it was rated as ◎. And those rated as △ or above were considered qualified. The evaluation of the EMPA116 contaminated cloth was carried out at washing temperatures of 60 °C, 70 °C, and 80 °C. Regarding the washing rate of the EMPA116 contaminated cloth, when the average value of the washing rates of 4 contaminated cloths was less than 25%, it was rated as ×; when it was 25% or more and less than 30%, it was rated as △; when it was 30% or more and less than 35%, it was rated as ○; when it was 35% or more, it was rated as ◎. And those rated as △ or above were considered qualified.

[0045] <Foam disappearance during rinsing> 4 ml of the cleaning solution after the above cleaning test was sampled into a mayonnaise bottle with a height of about 10 cm and a volume of about 200 ml, and the volume was adjusted to 100 ml with water having a Ca hardness of 60. After sealing, the container was shaken up and down in the vertical direction at a constant speed 40 times in 10 seconds and then immediately placed on a flat table. The foam height immediately after standing was measured, and when the foam height was less than 5 mm after 5 seconds, it was rated as ○; when it was 5 mm or more, it was rated as ×.

[0046] The results are shown in Tables 2 and 3.

[0047]

Table 2

[0048]

Table 3

[0049]

Table 4

[0050]

Table 5

[0051]

Table 6

[0052]

Table 7

[0053]

Table 8

[0054] As shown in Table 2, all of the compositions of the present invention were excellent in appearance stability. Also, as shown in Table 3, all of the compositions of the present invention (Compositions 1 to 23) showed excellent washing performance at temperatures of 60°C or higher in both the wet artificial stain cloth washing test and the EMPA 116 stain cloth washing test (Examples 1 to 30).

[0055] On the other hand, those using proteases that do not meet the requirements (1) to (3) of the present invention (Compositions 24 to 29, 34 to 36) were not suitable for use at temperatures of 60°C or higher, especially in the EMPA116 soiled cloth detergency test (Comparative Examples 1 to 6, 11 to 13). Also, those using an anionic surfactant instead of a nonionic surfactant (Compositions 30, 31), those using a protease that meets the requirements (1) to (3) of the present invention alone (Composition 33), and those using a nonionic surfactant alone (Composition 32) were inferior in detergency in the wet artificial soiled cloth detergency test or the EMPA116 soiled cloth detergency test at temperatures of 60°C or higher (Comparative Example 7, 8; Comparative Example 10; Comparative Example 9).

[0056] From the above results, by using a composition containing a protease having all three characteristics: (1) the activity value at pH 12.0 is 85% or more of the activity value at the optimum pH; (2) the activity value when 0.2% by mass of EDTA-4Na is added is 90% or more of the activity value without the addition of EDTA-4Na; and (3) the optimum temperature is 60°C or higher, and a nonionic surfactant, it was confirmed that excellent detergency for clothing can be demonstrated.< / ph>

Claims

Claim 1 (1) The activity value at pH 12.0 is 85% or more of the activity value at the optimum pH; (2) The activity value when 0.2% by mass of EDTA-4Na is added is 90% or more of the activity value when no EDTA-4Na is added; (3) The optimum temperature is 60°C or higher A liquid laundry detergent composition comprising a protease (excluding Esperase (registered trademark)) having all three characteristics and a nonionic surfactant, wherein the nonionic surfactant is an alkylene oxide adduct of a higher alcohol having a Griffin HLB value of 13 to 15 (either alone or two or more kinds, and in the case of two or more kinds, the sum of the values obtained by multiplying each HLB value by its respective mass ratio may be 13 to 15) and an alkylene oxide adduct of distyrenated phenol. The liquid laundry detergent composition for clothing (excluding those containing 0.05 to 3% by mass of amylase and bicarbonate, or those containing amylase and one or more organic solvents selected from the group consisting of phenoxyethanol, phenoxyisopropanol, and phenyl diglycol). Claim 2 The liquid laundry detergent composition for clothing according to claim 1, further comprising a fatty acid or a fatty acid salt. Claim 3 The liquid laundry detergent composition for clothing according to claim 1 or 2, further comprising a chelating agent. Claim 4 A washing method for washing clothes using the liquid laundry detergent composition according to any one of claims 1 to 3. Claim 5 The washing method according to claim 4, wherein the washing is performed at a temperature of 55°C or higher and under alkaline conditions. Claim 6 The washing method according to claim 5, wherein the washing is performed at a temperature of 60 to 80°C. Claim 7 The washing method according to claim 5 or 6, wherein the washing is performed under the condition of pH 9.0 to 13.0.

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