JP2011213992A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for washing which has excellent detergency and is excellent in both foamability and rinsability.SOLUTION: The liquid detergent composition includes (A) a polyoxyalkylene alkyl ether sulfate, (B) an alkylbenzene sulfonate, (C) a fatty acid and/or a salt thereof, (D) a compound having a pKa of 8.0 or more, and water, wherein the mass ratio of (A)/(B) is 85/15 to 30/70; the mass ratio of [(A)+(B)]/(C) is 85/15 to 30/70; the mass ratio of [(A)+(B)]/(D) is 85/15 to 40/60; the content of a nonionic surfactant is 2 mass% or less; and pH measured at 25°C according to JIS K 3362:1998 is 9.0 to 10.5.

Description

  The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition suitable for hand-washing laundry.

  There are two types of washing methods for clothing and the like: hand washing and washing machine washing. In recent years, there is a tendency for washing machines to increase due to the spread of washing machines. However, from the viewpoint of being able to confirm the degree of dirt removal and economical efficiency, hand washing is still widely performed worldwide. Yes. In particular, hand-washing laundry is often adopted so that it can be washed with as little water as possible in an area where water resources are low.

  Compared to washing with a washing machine, hand-washed washing enables fine washing according to the situation, such as the degree of dirt removal and the type of object to be washed. Accompanied by. In particular, “rubbing” in which objects to be cleaned are rubbed together is one of the most natural hand washing methods because it is easy to apply mechanical force to the parts to be cleaned.

  The amount of foam generated at the time of washing clothes and the like is a factor that causes a sense of fulfillment and a sense of security that washing is sufficient for consumers who do laundry. Many detergents mainly composed of anionic surfactants such as alkylbenzene sulfonates are manufactured and sold.

  On the other hand, as cleaning compositions for washing, granular (solid) and liquid compositions are mainly known. The liquid detergent composition has advantages such as no generation of fine powder during use and quick dissolution and dispersion in washing water.

  Patent Document 1 discloses a surfactant system including a specific anionic surfactant and a specific nonionic surfactant mixture, a detergency builder, and an auxiliary detergent component for use in a hand washing operation. A laundry detergent composition which can be in the form of a liquid is disclosed. Patent Document 2 discloses a hand-washing laundry detergent composition that can take the form of a liquid containing an anionic surfactant, a nonionic surfactant, and a cationic surfactant under specific conditions. Patent Document 3 discloses an aqueous liquid detergent composition containing a specific surfactant, a higher fatty acid salt, a sulfonate of benzene or lower alkylbenzene, an inorganic builder, and an alkali salt of a polyvalent carboxylic acid. .

Japanese National Patent Publication No. 10-504049 Japanese National Patent Publication No. 10-504056 JP-A-52-82909

  In addition to having an excellent detergency, a washing detergent composition for washing is desired to have excellent foaming properties that exhibit appropriate foaming during washing and excellent rinsing properties such as foam disappearing quickly during rinsing. Although Patent Documents 1 and 2 are said to have good foaming properties and low irritation properties, they have not yet sufficiently achieved rapid foam disappearance during rinsing. Although patent document 3 is supposed to be excellent in washing | cleaning property and stability, it cannot achieve coexistence of moderate foaming and quick foam disappearance in hand-washing washing.

  An object of the present invention is to provide a liquid detergent composition for washing that has excellent detergency in washing clothes and the like and is excellent in both foaming and rinsing properties.

  The present invention comprises (A) polyoxyalkylene alkyl ether sulfate ester salt (hereinafter referred to as component (A)), (B) alkylbenzene sulfonate salt (hereinafter referred to as component (B)), (C) fatty acid and / or its Salt (hereinafter referred to as component (C)), (D) a compound having a pKa of 8.0 or more, preferably 9.0 to 10.6 (hereinafter referred to as component (D)), and water, ) / (B) has a mass ratio of 85/15 to 30/70, and [(A) + (B)] / (C) has a mass ratio of 85/15 to 30/70, [(A) + (B)] / (D) is a mass ratio of 85/15 to 40/60, the content of the nonionic surfactant is 2% by mass or less, and the measurement is performed at 25 ° C. described in JIS K3362: 1998. The present invention relates to a liquid detergent composition having a pH of 9.0 to 10.5. In addition, as for the quantity of (A) component, (B) component, and (C) component, mass% and mass ratio shall respectively calculate by the quantity of sodium salt conversion, respectively.

  In the present invention, (A) polyoxyalkylene alkyl ether sulfate salt, (B) alkylbenzene sulfonate, (C) fatty acid and / or salt thereof (hereinafter referred to as (C) component), (D) pKa is 9. A compound containing 0 to 10.6 and water, the mass ratio of (A) / (B) is 85/15 to 30/70, and the mass ratio of [(A) + (B)] / (C) Is 85/15 to 30/70, the mass ratio of [(A) + (B)] / (D) is 85/15 to 40/60, and the content of the nonionic surfactant is 2% by mass. A liquid detergent composition having a pH of 9.0 to 10.5 measured at 25 ° C. described in JIS K3362: 1998 is included.

  The present invention is also a hand-washing washing method for hand-washing an object to be cleaned that has been brought into contact with the cleaning water containing the liquid detergent composition of the present invention, wherein the mass of the cleaning water relative to the mass of the object to be cleaned is 2-100. It is related to the hand-washing washing method.

  ADVANTAGE OF THE INVENTION According to this invention, in washing | cleaning of clothes etc., it has the outstanding cleaning power, and the liquid detergent composition excellent in both foaming property and rinse property is provided.

<(A) component>
(A) Although it does not specifically limit as polyoxyalkylene alkyl ether sulfate ester salt of a component, For example, C10-20, Preferably it is a 12-14 alkyl group, Preferably it is linear primary alcohol or It has an alkyl group derived from a linear secondary alcohol or an alkyl group derived from a branched alcohol, and an average addition mole number of an alkyleneoxy group is 0 to 5, preferably 0.5 to 4, more preferably 1 to 3. Can be mentioned. The component (A) preferably contains an ethyleneoxy group as an alkyleneoxy group, and may contain a propyleneoxy group in the range of an average addition mole number of 0.2 to 2 mol. The salt is preferably an alkali metal salt, particularly preferably a sodium salt and / or potassium salt, and particularly preferably a sodium salt.

<(B) component>
The alkylbenzene sulfonate of component (B) is not particularly limited, and examples thereof include alkyl benzene sulfonates having 8 to 20 carbon atoms, preferably 10 to 15 carbon atoms, and preferably having a linear alkyl group. .

  Examples of the alkylbenzene sulfonate include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of detergency and storage stability of the composition. , An alkali metal salt, or an alkanolamine salt is preferable. When preparing the composition of the present invention, an alkylbenzene sulfonic acid (acid type) is added to the composition, and it may be neutralized with an alkali in the system to obtain an alkyl benzene sulfonate. It may be added to the product. For neutralization of the alkylbenzene sulfonic acid, a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or the component (D) described later can be used.

<(C) component>
(C) Although it does not specifically limit as a fatty acid and / or its salt of a component, For example, C7-43, Preferably it is 9-23, More preferably, it is a linear or branched alkyl of 11-17. The thing which has group, More preferably, the C12-C14 fatty acid which has a linear or methyl branched chain, and / or its salt are mentioned. The component (C) may have an unsaturated bond, but the number thereof is 2 or less, preferably 1 or less, more preferably 0 from the viewpoint of rinsing properties. Specific examples of the component (C) include lauric acid and / or a salt thereof, myristic acid and / or a salt thereof, a mixture of lauric acid and fatty acid derived from coconut rich in myristic acid, and / or a salt thereof. In particular, from the viewpoints of detergency, foamability and rinsability, it is preferable to contain lauric acid and / or a salt thereof, or myristic acid and / or a salt thereof, and further contain myristic acid and / or a salt thereof. More preferred.

  The fatty acid salt of component (C) is preferably an alkali metal salt such as sodium or potassium, or an alkanolamine salt from the viewpoint of rinsing properties. When preparing the composition of the present invention, a fatty acid (acid type) may be added to the composition and neutralized with an alkali in the system, or after neutralization in advance and added to the composition. Also good. For the neutralization of the fatty acid, a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonium hydroxide or a component (D) described later can be used.

<(D) component>
If the component (D) is a compound having a pKa of 8.0 or more, preferably 8.0 to 10.6, more preferably 9.0 to 10.6, still more preferably 9.3 to 10.6, Although not limited, For example, alkali metal carbonates, such as potassium carbonate and sodium carbonate, and / or an alkanolamine, Especially the alkanolamine which has 1 to 3 C2-C4 alkanol groups can be mentioned. Of these, the alkanol group is preferably a hydroxyethyl group. Although it is a hydrogen atom other than an alkanol group, even if it is a C1-C5 alkyl group, especially a methyl group, it can be used as (D) component. As alkanolamine, 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned. In the present invention, alkanolamine is preferable, monoethanolamine or triethanolamine is more preferable, and monoethanolamine is most preferable from the viewpoint of detergency.

  Furthermore, it is preferable to use these alkanolamines in combination with alkali metal carbonates such as potassium carbonate from the viewpoint of improving the storage stability.

  The component (D) may be used for neutralizing the components (B) and (C) described above. From the viewpoint of detergency and low irritation to the hand skin, it is preferable that the pH buffering ability of the liquid detergent composition of the present invention is well expressed in the range of pH 9.0 to 10.5. It is desirable to combine a weak acid such as component C) with a compound having pKa as component (D) in the range of 9.0 to 10.6.

<Liquid cleaning composition>
The liquid detergent composition of the present invention has a mass ratio of (A) / (B) of 85/15 to 30/70, preferably 80/20 to 40/60, and more preferably 75/25 to 50 / 50, and 70/30 to 55/45. If the ratio of the component (A) in this mass ratio is within this range, the rinsability is improved particularly if it is 85/15 or less, while the washability is improved if it is 30/70 or more, and Excellent foaming properties when washing.

  In the liquid detergent composition of the present invention, the mass ratio of [(A) + (B)] / (C) is from the viewpoint of appropriate foaming properties during cleaning, quick foam disappearance during rinsing, and cleaning properties. It is 85 / 15-30 / 70, Preferably it is 80 / 20-45 / 55, More preferably, it is 75 / 25-55 / 45, More preferably, it is 70 / 30-60 / 40.

  In the liquid detergent composition of the present invention, [(A) + (B)] / () from the viewpoint of moderate foaming property during cleaning, cleanability and low irritation to the hand skin, particularly from the viewpoint of foaming property. The mass ratio of D) is 85/15 to 40/60, preferably 82/18 to 50/50, more preferably 79/21 to 55/45, more preferably 76/24 to 60/40, and more preferably Is 73/27 to 65/35.

  In the liquid detergent composition of the present invention, the component (B) is 0.5 to 20% by mass, further 1.2 to 12% by mass, further 2 to 8% by mass, and further 2.2 to 7.5% by mass. %, And more preferably 3 to 5% by mass. Further, the component (C) is calculated in terms of sodium salt and contained in an amount of 1 to 50% by mass, further 1.5 to 30% by mass, further 2 to 20% by mass, and further 4 to 10% by mass. preferable. Moreover, it is preferable to contain (D) component 2-10 mass%, Furthermore, 2.5-8 mass%, Furthermore, 3.5-6 mass%, Furthermore, 3.8-5.5 mass% is contained. The content of each component is selected within a range that satisfies the mass ratio.

  The liquid detergent composition of the present invention has a total of 5 to 30% by mass of the component (A) and the component (B), and further 6 to 20% from the viewpoint of moderate foaming properties and quick foam disappearance at the time of rinsing. It is preferable to contain 7 mass%, further 7-15 mass%, and further 8-12 mass%. If this content is 5% by mass or more, a composition having better detergency and foaming properties can be obtained. On the other hand, if it is 30% by mass or less, it has a good viscosity and dissolves and disperses quickly in the washing liquid. Or a composition having a clear liquid feeling is obtained.

  In the liquid detergent composition of the present invention, the content of water is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably 50 to 80% by mass in the composition.

  In the liquid detergent composition of the present invention, the content of the nonionic surfactant is 2% by mass or less, 1.5% by mass or less, and further 1% by mass or less from the viewpoint of rapid foam extinction at the time of rinsing. More preferably, it is 0.5% by mass or less, and further, it is not blended at all, that is, the liquid detergent composition of the present invention does not contain a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant said here, For example, a polyoxyalkylene alkyl ether is mentioned, for example, for example, it is 4-15 on the average for ethylene oxide to C10-C18 alcohol, Preferably 4-10 mol, the polyoxyalkylene alkyl ether which added 0-5 mol of propylene oxide on the average is mentioned, It is preferable to keep the content within the said range. In general, such nonionic surfactants have high orientation to the gas-liquid interface, and c. m. c. Since the (critical micelle concentration) is small, bubbles remain persistently even at low concentrations, impeding rapid bubble disappearance during rinsing. However, among polyoxyalkylene alkyl ethers, those having a large addition mole number of alkylene oxide, for example, an average of more than 15 moles of ethylene oxide in an alcohol having 10 to 18 carbon atoms, preferably an average of 20 moles or more, and 0 on average of propylene oxide. The added amount of ˜5 mol may be used in the liquid detergent composition of the present invention as long as it is a small amount (desirably 2% by mass or less).

  The liquid detergent composition of the present invention, as a nonionic surfactant, has an average of 4 to 60 mol, preferably 4 to 30, more preferably 4 to 15, more preferably ethylene oxide in an alcohol having 10 to 18 carbon atoms. Can also contain 4 to 10 moles of polyoxyalkylene alkyl ether with 0 to 5 moles of propylene oxide added on average.

  Here, when using polyoxyalkylene alkyl ether in which ethylene oxide is added to alcohol having 10 to 18 carbon atoms on average in an amount of 4 to 15 moles, preferably 4 to 10 moles, and propylene oxide in an average of 0 to 5 moles is rinsed. From the viewpoint of rapid foam extinction, the content of the polyoxyalkylene alkyl ether in the liquid detergent composition of the present invention is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further It is most desirable that it is 1% by mass or less, further 0.5% by mass or less, and further not blended at all, that is, the liquid detergent composition of the present invention does not contain the polyoxyalkylene alkyl ether. Therefore, in the present invention, the nonionic surfactant whose content in the composition is limited to 2% by mass or less is an average of 4 to 15 mol, preferably 4 to 4, of ethylene oxide in an alcohol having 10 to 18 carbon atoms. The polyoxyalkylene alkyl ether which added 10 mol and 0-5 mol of propylene oxide on the average may be sufficient.

On the other hand, the liquid detergent composition of the present invention comprises a polyoxyalkylene alkyl ether prepared by adding an average of more than 15 to 60 mol of ethylene oxide and an average of 0 to 5 mol of propylene oxide to an alcohol having 10 to 18 carbon atoms. It can contain in the range which does not inhibit the effect of invention, desirably 2 mass% or less. The liquid cleaning composition of this invention can contain the nonionic surfactant represented by the following general formula (e1) as (E) component.
_{^{R 1e O - [(C 2}} H 4 O) m / (C 3 H 6 O) n] H (e1)
[Wherein, R ^1e is a hydrocarbon group having 10 to 18 carbon atoms. m and n are average added mole numbers, m is a number of more than 15 to 60, and n is a number of 0 to 5. “/” Indicates that the C ₂ H ₄ O group and the C ₃ H ₆ O group may be bonded to either random or block. ]

In the general formula (e1) of the component (E), R ^1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms. R ^1e is preferably a chain hydrocarbon group, and more preferably a linear hydrocarbon group. The hydrocarbon group for R ^1e is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ^1e is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the present invention, the carbon atom of R ^1e bonded to the oxygen atom may be the first carbon atom. Such an alkyl group can use a fatty alcohol derived from natural fats and oils as a raw material. The compound in which the carbon atom of R ^1e bonded to the oxygen atom of R ^1e —O— in the general formula (e1) is the first carbon atom is superior in the detergency than the compound having the second carbon atom. In particular, R ^1e is preferably a linear alkyl group having the first carbon atom.

  The method for obtaining the compound of the general formula (e1) is not particularly limited, but it can be obtained by addition reaction of ethylene oxide with an alcohol having 10 to 18 carbon atoms or addition reaction of ethylene oxide and propylene oxide. it can.

  M in the general formula (e1) is the average number of added moles of ethyleneoxy group, and the lower limit of m is preferably 18 or more, more preferably 20 or more, more preferably from the viewpoint of rinsing properties and cleaning performance. It is 22 or more, more preferably 26 or more, more preferably 30 or more, and the upper limit is preferably 45 or less, more preferably 35 or less, from the viewpoint of ease of production. Accordingly, as the component (E), a nonionic surfactant having a number m in the general formula (e1) of 18 to 60, preferably 26 to 60 can be used. n is the average number of moles of propyleneoxy group added, and the lower limit is 0 or more, preferably 1 or more, and the upper limit is 5 or less, preferably 4 or less, more preferably 3 or less, from the viewpoint of cleaning performance.

  The propyleneoxy group in the general formula (e1) has a methyl branched structure in the case of addition reaction of propylene oxide.

By the way, in the case of a structure in which C ₃ H ₆ O is present at a position close to R ^1e O—, since C ₃ H ₆ O is a hydrophobic group, a structure in which a chain hydrocarbon group as R ^1e is extended. It shows a tendency to increase the hydrophobicity. In the general formula (e1), the component (E) of the present invention is such that the proportion of the compound that is R ^1e —O—C ₂ H ₄ O— is 75 mol% or more in the compound constituting the component (E). Furthermore, it is preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound can also be obtained by removing the unreacted alcohol. In the present invention, particularly, 6 mol or more, particularly 8 mol or more of ethylene oxide is added to 1 mol of R ^1e OH. The requirement can be achieved. This rule may be applied to general formulas (e1-2), (e1-4), and (e1-5) described later.

Furthermore, in the general formula (e1), the component (E) satisfies the above-described condition of R ^1e —O—C ₂ H ₄ O—, and the proportion of the terminal is —C ₂ H ₄ O—H. high is than if terminus is -C ₃ H ₆ O-H propyleneoxy group of the hydrophobic group, preferably from the low absorptive fibers. In particular, it is more preferable that the compound having a structure having a terminal —C ₂ H ₄ O—H is 70 mol% or more, and more preferably 80 mol% or more (the upper limit is 100 mol% or less). Such a compound is produced by first adding ethylene oxide under the above-mentioned conditions in the production of the general formula (e1), or after adding ethylene oxide, removing unreacted alcohol, and then propylene oxide, preferably propylene. It can be obtained by conducting an oxide addition reaction step and finally adding only 6 mol or more, particularly 8 mol or more of ethylene oxide. This rule may be applied to general formula (e1-5) described later. The ratio of R ^1e —O—C ₂ H ₄ O— or —C ₂ H ₄ O—H can be determined by quantitative measurement using C ¹³ -NMR.

The compound represented by the general formula (e1) of the present invention may be compounds represented by the following general formulas (e1-1) to (e1-5). The compounds represented by the general formulas (e1-1) to (e1-5) can be prepared by considering the reaction ratio and reaction sequence of alkylene oxide with respect to R ^1e OH.
_{^{R 1e O- (PO) n -}} (EO) m H (e1-1)
_{^{R 1e O- (EO) m -}} (PO) n H (e1-2)
^{R 1e O - [(EO)} m1 · (PO) n] - (EO) m2 H (e1-3)
_{^{R 1e O- (EO) m1 -}} [(PO) n · (EO) m2] H (e1-4)
_{^{R 1e O- (EO) m1 -}} (PO) n - (EO) m2 H (e1-5)
[In the formula, EO and PO are an ethyleneoxy group and a propyleneoxy group, respectively, R ^1e , m, and n have the same meanings as described above, and m1 and m2 are average added mole numbers, and m = m1 + m2. “·” Indicates a random bond. ]

  In the present invention, the compound of the general formula (e1-2), (e1-4) or (e1-5), particularly the compound of the general formula (e1-2) or (e1-5) is more preferable from the viewpoint of rinsing properties. preferable.

The component (E) of the present invention is a compound represented by R ^1e —OH (R ^1e is a hydrocarbon group having 10 to 18 carbon atoms, preferably the same as R ^1e in the general formula (e1)) per mole. A nonionic surfactant obtained by adding m1 mol of ethylene oxide, then adding n mol of propylene oxide, and then adding m2 mol of ethylene oxide, wherein m1 is a number of 3 to 30, preferably 5 to 25, more preferably 8 to 20, n is a number of 1 to 5, preferably 1 to 3, and m1 and m2 are in total m1 + m2 = 18 to 60, preferably 22 to 45. A nonionic surfactant having a number of 26 to 35 is more preferable. Although m2 can be calculated | required from said m1 and m1 + m2, m2 becomes like this. Preferably it is a number of 3-30, More preferably, it is a number of 7-25, Preferably it is a number of 8-20. In the present invention, it is particularly preferable that PO is not bonded to the terminal and R ^1e , and m1 and m2 are preferably m1 / (m1 + m2) = 0.2 to 0.8, more preferably 0.3 to 0.7. In this case, R ^1e , m1, m2 and n have the same meaning as in the general formula (e1-5).

Regarding the production of the component (E), examples of the catalyst used for alkoxylation of R ^1e —OH include a base catalyst and an acid catalyst. Of these, a base catalyst is preferably used from the viewpoint of cost, sodium hydroxide or potassium hydroxide is more preferable as the base, and potassium hydroxide is most preferably used.

An example of production conditions when potassium hydroxide is used as a catalyst is shown below. First, potassium hydroxide is charged into a higher alcohol having 10 to 18 carbon atoms (compound represented by R ^1e —OH) as a raw material, followed by replacement with nitrogen, and 30 to 1 hour at 100 to 110 ° C. and 1 to 7 kPa. Perform dehydration. Then, addition of ethylene oxide at 100 to 170 ° C. and 0.3 to 0.6 MPa, followed by addition of propylene oxide under the conditions of 100 to 150 ° C. and 0.3 to 0.7 MPa, again 100 to 170 ° C., After adding ethylene oxide under the condition of 0.3 to 0.7 MPa, it is obtained by neutralizing with added potassium hydroxide and an equimolar amount of an acid agent (acetic acid, lactic acid, glycolic acid, etc.). In addition, the usage-amount of each ethylene oxide and propylene oxide is selected according to the number-of-moles of raw material alcohol so that the conditions of the average value of m and n in a composition may be satisfy | filled.

  In addition, the liquid detergent composition of the present invention has the effect of the present invention as a component (F) with surfactants other than the components (A), (B), (C) and the nonionic surfactant. It can contain in the range which is not impaired. In the present invention, the proportion of the component (F) is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less in the total surfactant.

  The component (F) is not particularly limited, and examples thereof include aliphatic alcohols, alkanolamides, amine oxides, and betaines. Since these have a function as a foam booster, for example, as described in “Foam Engineering” (published by Techno System Co., Ltd., 2005), the foaming power of the cleaning composition of the present invention is increased. be able to. Among the components (F), the foam booster selected from aliphatic alcohol, alkanolamide, amine oxide, and betaine is 5% by mass or less, more preferably 3% by mass in the total surfactant in order not to impair the rinsing property. Hereinafter, it is more preferably 1.5% by mass or less.

  Examples of the aliphatic alcohol include aliphatic alcohols having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms. Among these, dodecyl alcohol is preferable. As the alkanolamide, monoethanolamide, diethanolamide, N-methylethanolamide and the like are preferable, but those having an isopropanolamide type or an alkylene oxide added thereto can be used. Examples of the amine oxide include mono long chain alkyl amine oxides having a long chain length alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, and an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. be able to. Examples of betaines include alkylamidopropyl betaines. Among them, lauramidopropyl betaine having 12 carbon atoms and cocoamidopropyl betaine having a coconut oil composition are generally used.

  In particular, from the viewpoint of foaming power and rinsability, the component (F) is selected from (F1) a compound represented by the following general formula (f1) and (F2) a compound represented by the following general formula (f2). It is preferable to use a surfactant. Two or more of these can be used.

[Wherein, R ^1f is a hydrocarbon group having 9 to 23 carbon atoms, and R ^2f is an alkylene group having 1 to 6 carbon atoms. X is a group selected from an ester group, an amide group, and an ether group, and p is a number of 0 or 1. R ^3f and R ^4f are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^5f is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. It is. Y ^- is an anionic group. ]
R ^6f- (OR ^7f ) _q -OH (f2)
[Wherein R ^6f is a hydrocarbon group having 6 to 18 carbon atoms, R ^7f is a residue obtained by removing two hydroxy groups from a propylene group or glycerin, and q is a number of 1 to 5. ]

The component (F1) is a compound represented by the general formula (f1). In the general formula (f1), R ^1f is a hydrocarbon group having 9 to 23 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group having 10 to 15 carbon atoms, and more preferably 11 to 13 carbon atoms. R ^2f is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 3 carbon atoms. X is a group selected from an ester group, an amide group, and an ether group, and specifically includes a group selected from -COO-, -OCO-, -CONH-, -NHCO-, and -O-. . X is preferably an amide group, and more preferably a group represented by -CONH-. p is preferably 0 or 1. R ^3f and R ^4f are each preferably a methyl group or a hydroxyethyl group, more preferably a methyl group. Y ⁻ is an anionic group, and examples thereof include a group selected from —SO ₃ ⁻ , —OSO ₃ ⁻ , and —COO ⁻ . Y ⁻ is preferably —SO ₃ ^— or —COO ^— , and when Y ⁻ is —SO ₃ ^— , R ^5f is preferably —CH ₂ CH (OH) CH ₂ —, and Y— is —COO ^— . R ^5f is preferably a methylene group (—CH ₂ —).

The component (F2) is a compound represented by the general formula (f2). The compound of the general formula (f2) is suitable for increasing the foaming power, but at the same time, it is desired that the rinsing property is also good. In order to make these compatible, it is preferable that both the hydrophilic group structure and the hydrophobic structure of the compound represented by the general formula (f2) are limited as follows. Although it is not necessarily certain, it is considered that the orientation to the gas-liquid interface is higher than the orientation to clothing and dirt by adopting the following structure. In the general formula (f2), R ^6f is preferably an alkyl group or an alkenyl group having 6 to 18 carbon atoms, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms. When R ^7f is a propylene group, q is preferably 2 to 4 from the viewpoint of foamability and rinsing properties. From the same viewpoint, when R ^7f is a residue obtained by removing two hydroxy groups from glycerin, q is preferably 1 to 3, and more preferably 1. R ^7f is preferably a residue obtained by removing two hydroxy groups from glycerin.

As the component (F2), R ^6f in the general formula (f2) is an alkyl group or alkenyl group having 6 to 10 carbon atoms, R ^7f is a residue obtained by removing two hydroxy groups from glycerin, and glyceryl ether having q = 1 Is preferred. For example, 2-ethylhexyl monoglyceryl ether, isononyl monoglyceryl ether, isodecyl monoglyceryl ether, etc. are mentioned. In particular, 2-ethylhexyl monoglyceryl ether is preferable for achieving both foamability and rinsing properties.

  In the liquid detergent composition of the present invention, from the viewpoint of foamability and rinsing properties, the component (F1) is 0.1 to 10% by mass, further 0.2 to 5% by mass, and further 0.4 to 2.%. It is preferable to contain 7 mass%.

  Moreover, the liquid detergent composition of this invention is 0.1-10 mass% of (F2) component from a viewpoint of foamability and a rinse property, Furthermore, 0.2-5 mass%, Furthermore, 0.4- It is preferable to contain 2.7 mass%.

  Moreover, the liquid cleaning composition of this invention can contain both (F1) component and (F2) component from a foamable viewpoint. At this time, the mass ratio of (F1) / (F2) is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and even more preferably 60/40 to 40/60.

  The liquid detergent composition of the present invention has a pH of 9.0 to 10.5, preferably 9.3 as measured at 25 ° C. described in JIS K3362: 1998, from the viewpoint of detergency and mildness to hand skin. -10.2, more preferably 9.5-10. The pH can be adjusted depending on the type and amount of the component to be blended in the composition, and in particular, the type and blending amount of the component (B), the component (C), and the component (D). You may adjust using acid agents, such as 6N-HCl).

  The liquid detergent composition of the present invention has an excellent detergency in washing clothes and the like by specifying the mass ratio of each component and the content of the nonionic surfactant described above, and has a foaming property. It exhibits excellent performance in both rinsing properties.

  Examples of other components that can be incorporated into the liquid detergent composition of the present invention include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, and triethylenetetraamine. Aminopolyacetic acid such as hexaacetic acid and diencoric acid or salts thereof, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid Chelating agents such as organic acids such as carboxymethyl tartaric acid or salts thereof, preferably chelating agents having a molecular weight of 1,000 or less can be blended. It is preferable that content of a chelating agent is 0.001-10 mass%, 0.01-3 mass%, and 0.03-1 mass% in a composition.

  In addition, it is preferable to contain a water-miscible organic solvent [hereinafter referred to as component (G)] for the purpose of improving the solution stability and transparency of the cleaning composition. The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, a solvent having a degree of dissolution of 50 g / L or more. The content of the component (G) is 0.5 to 40% by mass, further 1 to 20% by mass, more preferably 1.5 to 10% by mass in the composition from the viewpoint of improving the solution stability and transparency. Furthermore, 2-5 mass% is preferable.

  As the component (G), (G1) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (G2) glycols such as propylene glycol, butylene glycol and hexylene glycol, (G3) diethylene glycol, Glycols such as triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, (G4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, tripropylene glycol Methyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3-diethyl Alkyl ethers such as glycerin ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, diethylene glycol monobutyl ether (also called butoxy diglycol), (G5) 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol having an average molecular weight of about 480 Mono phenyl ether, 2-benzyloxy ethanol, aromatic ethers such as diethylene glycol monobenzyl ether, and the like.

  The water-miscible organic solvent is effective at the same time as a viscosity modifier and gelation inhibitor of the composition, and the above (G1) alkanols, (G2) glycols, (G4) alkyl ethers, (G5) aromatics It is preferable to use one or more selected from ethers, more preferably selected from (G2) glycols, (G4) alkyl ethers, and (G5) aromatic ethers, particularly preferably (G4). It is. In particular, diethylene glycol monobutyl ether is preferable. The component (G) is effective for adjusting the viscosity and suppressing gelation.

  As other components that can be blended in the liquid detergent composition of the present invention, the following components (i) to (xiii) can be blended to such an extent that the effects of the present invention are not impaired.

(I) Polyacrylic acid, polymaleic acid, carboxymethyl cellulose, polyethylene glycol having a weight average molecular weight of 5,000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate Prevention of recontamination of copolymers, naphthalenesulfonate formalin condensates, and polymers described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614 Agents and dispersants 0.1-10% by weight, preferably 0.5-5% by weight, more preferably 1-3% by weight
(Ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate (iv) Tetraacetylethylenediamine, general formula (I-2) of JP-A-6-316700 Bleach activators such as bleach activators represented by (I-7) (v) Enzymes such as cellulase, amylase, pectinase, protease, lipase (vi) Boron compounds, calcium ion sources (calcium ion supply compounds) Enzyme stabilizers (vii) fluorescent dyes such as bihydroxy compounds and formic acid, for example, fluorescent dyes commercially available as Chino Pearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (Viii) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite (X) Solubilizers such as antioxidants (ix) paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, benzoates (also effective as preservatives) (x) having an average molecular weight of about 200 to about 400 Polyalkylene glycol-based anti-gelling polymers such as polyethylene glycol and polypropylene glycol having an average molecular weight of about 1,000 to about 2,000 (xi) Paraffins such as octane, decane, dodecane and tridecane, and olefins such as decene and dodecene Water-immiscible organic solvents such as halogenated alkyls such as methylene chloride and 1,1,1-trichloroethane, and terpenes such as D-limonene.
(Xii) Metal ion exchangers such as zeolite and crystalline layered silicate (xiii) Other antifoaming agents such as dyes, fragrances, antibacterial preservatives, and silicones

  In the liquid detergent composition of the present invention, for example, a predetermined amount of the components (A) and (D) and, if necessary, (G) in ion-exchanged water heated to a predetermined temperature (about 80 ° C.) Add ingredients and dissolve. If necessary, a strong base such as sodium hydroxide is added at this stage. Next, the acid type (B) component and the acid type (C) component are added and mixed until it becomes transparent, then other components are added as appropriate, and after cooling to room temperature, a fragrance, a pigment, and the like are added. be able to.

  The liquid detergent composition of the present invention is suitable for washing at home and also for hand washing, and is suitably used for hand washing of textile products such as clothing, cloth, bedding, towels and the like.

  The present invention relates to a hand-washing laundry method for hand-washing an object to be cleaned that has been brought into contact with cleaning water containing the liquid detergent composition of the present invention. Examples of the hand-washing washing method using the liquid detergent composition of the present invention include a method of hand washing by bringing the washing water containing the liquid detergent composition of the present invention into contact with an object to be washed such as a fabric and soaking. . When the contact time and / or immersion time is long, the cleaning effect is high, and when the contact time and / or immersion is 5 to 15 minutes, a better effect is obtained. In particular, when the composition is directly applied to a soiled portion and left for 5 to 15 minutes, a higher effect can be obtained. As the washing water, the composition of the present invention or a water dilution of the composition (for example, an aqueous solution) is used. The mass of washing water with respect to the mass of an object to be cleaned such as a fabric is preferably 2 to 100 times, more preferably 3 to 50 times, and particularly preferably 5 to 25 times. When the object to be cleaned such as the fabric brought into contact with the cleaning water according to the present invention is sufficiently rubbed by hand, not only a high detergency is obtained but also abundant foaming is visually preferred. After scrubbing, the fabric is taken out from the washing water, squeezed to drain the water, or drained using a dehydrator, and immersed again in fresh water (hereinafter referred to as rinsing water). The rinsing water may be either water stored in a basin or running water. The mass of rinsing water with respect to the fabric is preferably 2 to 1,000 times, more preferably 5 to 500 times, and particularly preferably 10 to 100 times based on the total amount of rinsing water used for rinsing. Since the surfactant remaining in the fabric at the stage of immersing the rinse water is redissolved in the rinse water, foaming is observed. When this operation is repeated several times, the foaming disappears and the rinsing is completed. In general washing by hand, for example, when a normal cleaning agent is used, it is generally required 5 times or more. However, in the present invention, rinsing can be completed in 3 times or less, and rinsing is performed with very little rinsing water. Can be terminated.

  The hardness of water used for the preparation of washing water and / or the hardness of rinsing water is preferably 1 ° DH to 50 ° DH, more preferably 2 ° DH to 40 ° DH, more preferably from the viewpoint of detergency and rinsing properties. Is 3 ° DH to 30 ° DH, more preferably 5 ° DH to 25 ° DH, more preferably 10 ° DH to 20 ° DH.

  A liquid detergent composition was prepared using the ingredients shown in Tables 1 and 2, and the following evaluations were performed. The results are shown in Tables 1 and 2.

(1) Evaluation of foaming property A circular washbasin (diameter 25 cm at the bottom, diameter 30 cm at the top, height 12 cm, Shinki Gosei Co., Ltd., Washing Type 33), water temperature 20 ° C., 179 mg / L in terms of calcium carbonate [Calcium chloride CaCl ₂ 1.19 g and magnesium sulfate MgSO ₄ .7H ₂ O 1.76 g added with ion exchange water to make 10 L, Ca / Mg = 7/3 (molar ratio), hard water is 10 in German hardness [Corresponds to DH] 3L is injected. 20g of liquid detergent composition is added there, and it is made to melt | dissolve uniformly, stirring by hand. Next, three underwears (Gungze Co., Ltd. (YG1614 round neck L size, made of cotton)) in which the adjustment oil shown below was uniformly dropped so as to be 0.5 g per sheet were thrown there, 15 After leaving for 15 minutes, wash 50 times with each undergarment (convert to 1 time in 1 reciprocation (approx. 1 second) while rubbing the cloth and cloth). Squeeze on the basin so that the amount of water is about 40-60% of the underwear, and check the condition of the washing liquid immediately after squeezing three. If it does not cover the entire surface of the washing liquid, it is expressed as the ratio of the area covered by the foam (for example, half the liquid level). If it is covered by bubbles, it is written as 1/2).

* Adjusted oil Lauric acid 1% by mass, myristic acid 7.1% by mass, pentadecanoic acid 5.3% by mass, palmitic acid 14.2% by mass, heptadecanoic acid 1% by mass, stearic acid 3.6% by mass, oleic acid 17 0.8% by mass, 30% by mass of triolein, 5% by mass of n-hexadecyl palmitate, and 15% by mass of squalene were heated to about 60 ° C., and uniformly dissolved and mixed.

(2) Rinse evaluation Hard water with a water temperature of 20 ° C. and calcium carbonate equivalent of 179 mg / L in a circular washbasin (diameter 25 cm at the bottom, diameter 30 cm at the top, height 12 cm, Shinki Gosei Co., Ltd., Wash 33) 5L is injected (prepared in the same manner as that used in the evaluation of foaming properties), and three underwears squeezed in the evaluation of foaming properties are introduced. After rinsing the underwear in the water, lift the loose underwear one by one from the bath (from the bath until all the clothes are removed), and then return to the bath again. After rinsing by such up-and-down movement is repeated 10 times for each undergarment, it is squeezed by hand so that the moisture content of the undergarment is about 40 to 60% of the undergarment. Rinse the three underwears and observe the level of the rinse water immediately after the dehydration is finished. New rinse water is added to the dehydrated underwear, and this evaluation is repeated two more times (three underwears are used for one liquid detergent composition, including the above-mentioned foaming property evaluation), and the rinsability is evaluated with the sum of points. did.
Point 6: Foam with a height of 1 cm or more remains on the entire liquid surface 5: Foam remains on the entire liquid surface (less than 1 cm)
4: Bubbles remain at about 1/2 of the liquid level 3: Bubbles remain at about 1/4 of the liquid level 2: Fine bubbles remain at the liquid level 1: Bubbles remain at the liquid level Absent

(3) Detergency evaluation <Production of artificially contaminated cloth>
Artificial stains used were 6cm x 6cm cotton / polyester blended broad-dyed fabric (cotton / polyester ratio = 65/35 purchased from Tanigami Shoten). Gravure coating.

* Artificial dirt The composition containing the following A, B, C, D, E was used as artificial dirt. Each mass% is a ratio in the artificial dirt of the final composition, and the amount of B was adjusted so that the total was 100 mass%.
A: Adjustment oil used in the evaluation of foaming properties (mass% in artificial dirt is 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 palmitic acid) Wt%, heptadecanoic acid 0.44 wt%, stearic acid 1.6 wt%, oleic acid 7.91 wt%, triolein 13.33 wt%, n-hexadecyl palmitate 2.22 wt%, squalene 6.66 (Use in an amount of mass%)
B: Hard water obtained by weighing 105 mg of calcium chloride (dihydrate) and dissolving in distilled water to obtain 1,000 ml C: 1.98% by mass of egg white lecithin liquid crystal (11.37 g of arginine hydrochloride, 80 ml of distilled water, histidine 4. After dissolving 20.20 g and 2.44 g of serine and adjusting the pH to 5.0 with concentrated hydrochloric acid, this solution and egg white lecithin were sufficiently mixed with a mixer to obtain an egg white lecithin liquid crystal product)
D: Kanuma red soil 8.11 mass%
E: Carbon black 0.025 mass%

<Cleaning conditions>
3 g of the liquid detergent composition is dissolved in 1 liter of hard water (prepared in the same manner as that used in the evaluation of foaming property) in terms of calcium carbonate, and 4 pieces of the above artificially contaminated cloth are added to the targot. Washing was performed with a meter under the following conditions.
Washing time 10 minutes Water temperature 20 ° C
Detergency was measured with a colorimetric colorimeter (Nippon Denshoku Co., Ltd., Z-300A) for the reflectance at 550 nm before and after washing, and the washing rate (%) was determined by the following formula. (The values in the table are average values of the cleaning rates of 4 sheets).
Washing rate (%) = 100 × [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)]

(4) Irritation test on hand skin After three healthy female panelists continuously performed the foaming property evaluation of (1) and the rinsing property evaluation of (2) with bare hands, the hand skin feel was evaluated. Evaluation was made according to the following criteria. Tables 1 and 2 show the average values of the three evaluation points.
(Evaluation points)
0: No particular discomfort in the hand skin 1: After washing, I felt a sense of tension 2: The hand skin was rough

The components in the table are as follows. Moreover, 6N-HCl was also used for pH adjustment as needed.
AES-Na: polyoxyethylene (average number of added moles 2) sodium lauryl ether sulfate (Emar 270J, manufactured by Kao Corporation)
LAS-Na: Sodium alkylbenzene sulfonate [Alkylbenzene (trade name: Alkene L, manufactured by Nippon Oil Corporation) was contacted with SO ₃ gas and sulfonated under the condition of a reaction molar ratio of SO ₃ /alkylbenzene=1.030. Alkylbenzenesulfonic acid was blended as a raw material, and neutralized with sodium hydroxide during the process of producing the composition. Here, the carbon number of the alkyl group is 10-13. ]
-Myristic acid: Table 1 shows mass% and mass ratio calculated in terms of sodium salt.
Nonionic surfactant (1): polyoxyethylene (average added mole number 8) alkyl (carbon number 10-14) ether Nonionic surfactant (2): polyoxyethylene (average added mole number 21) alkyl (C12) Ether F1-1: Sulfobetaine represented by the following formula, Amphital 20HD (manufactured by Kao Corporation)

F1-1: Betaine represented by the following formula, Amhitor 20AB (manufactured by Kao Corporation)

F2-1: 2-ethylhexyl monoglyceryl ether

  As shown in Table 1, in Examples 1 to 9 and Examples 10 to 14, excellent results were obtained in any evaluation. On the other hand, Comparative Examples 1, 6, and 8 are in terms of rinsing properties, Comparative Examples 2, 3, 7, and 9 are in terms of foaming properties and cleaning properties, and Comparative Examples 4 and 5 are in terms of foaming properties and irritation, It turned out that it is inferior to an Example.

Claims (10)

  (A) a polyoxyalkylene alkyl ether sulfate ester salt, (B) an alkylbenzene sulfonate, (C) a fatty acid and / or a salt thereof, (D) a compound having a pKa of 8.0 or more, and water, ) / (B) has a mass ratio of 85/15 to 30/70, and [(A) + (B)] / (C) has a mass ratio of 85/15 to 30/70, [(A) + (B)] / (D) is a mass ratio of 85/15 to 40/60, the content of the nonionic surfactant is 2% by mass or less, and the measurement is performed at 25 ° C. described in JIS K3362: 1998. A liquid detergent composition having a pH of 9.0 to 10.5.   The liquid detergent composition according to claim 1, wherein (A) is a polyoxyalkylene alkyl ether sulfate salt having an alkyl group having 10 to 20 carbon atoms and having an average addition mole number of alkyleneoxy groups of 0 to 5. object.   The liquid cleaning composition of Claim 1 or 2 which contains 2-8 mass% of (B).   The liquid detergent composition according to any one of claims 1 to 3, wherein (D) is a compound having a pKa of 9.0 to 10.6.   The liquid detergent composition according to any one of claims 1 to 4, wherein (D) is an alkali metal carbonate or alkanolamine having a pKa of 9.0 to 10.6.   The liquid cleaning composition in any one of Claims 1-5 which contains 5-30 mass% of (A) and (B) in total.   The liquid cleaning composition in any one of Claims 1-6 containing 1-50 mass% of (C).   The liquid cleaning composition in any one of Claims 1-7 which contains 2-10 mass% of (D).   The nonionic surfactant is a polyoxyalkylene alkyl ether obtained by adding an average of 4 to 15 mol of ethylene oxide and an average of 0 to 5 mol of propylene oxide to an alcohol having 10 to 18 carbon atoms. Liquid detergent composition.   It is a hand-washing washing method which carries out the hand washing of the to-be-washed object which contacted the wash water containing the liquid detergent composition in any one of Claims 1-9, Comprising: The mass of the wash water with respect to the mass of a to-be-washed object is 2-100 times Is a hand-washing washing method.