JP6052777B2 - Liquid detergent composition - Google Patents

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. On the other hand, large household items such as sheets are unsuitable for hand-washing, so many households use both hand-washing and washing machine washing.

  In both hand-washing and washing-machine washing, it is important to control foaming when washing and too much foaming when washing too much. For example, the amount of foam generated during washing of clothes, etc., is a factor that causes a sense of fulfillment and security that washing is sufficient for consumers who do laundry, Foam residue can also cause anxiety. Especially in the case of hand washing, some people increase the number of rinses if there is foam residue. Even in the case of washing with a washing machine, there are some people who show intense disgust or increase the number of times of rinsing with respect to the remaining foam during rinsing.

  In addition, in laundry such as clothing, in recent years, awareness of hygiene and cleanliness has increased, and functions such as deodorization and deodorization are required in addition to the original functions such as removal of dirt. Here, the deodorizing function refers to a function that suppresses unpleasant odor that occurs when the humidity is high and the laundry is difficult to dry. The excellent deodorizing function means, for example, that it does not cause unpleasant odors, does not feel unsanitary, does not feel anxious odors, even if it is in a bad environment such as a rainy day or indoors. When blended, it leads to a more hygienic feeling such as enjoying a good scent.

  In Patent Document 1, a liquid detergent composition containing a nonionic surfactant, a cationic surfactant, a hydrotrope agent, hydrogen peroxide, and a water-miscible solvent under predetermined conditions is used after washing clothes and the like. It is disclosed that a raw dry odor can be suppressed.

  Patent Document 2 discloses an injectable liquid laundry detergent composition containing a surfactant such as sodium alkyl ether sulfonate, sodium alkylbenzene sulfonate, sodium alkyl sulfonate, and the like.

  Patent Document 3 discloses a polyoxyalkylene alkyl ether type nonionic surfactant having a relatively large average number of added moles of alkyleneoxy groups, a specific anionic surfactant, and a fatty acid having 8 to 18 carbon atoms or a salt thereof. It is disclosed that the cleaning composition contained under specific conditions is excellent in cleaning power and foaming property at the time of cleaning, and the foam disappears quickly in the rinsing step, and the rinsing is completed quickly. .

  Patent Document 4 discloses a liquid cleaning containing polyoxyalkylene alkyl ether sulfate, alkylbenzene sulfonate, fatty acid and / or salt thereof under specific conditions, and a nonionic surfactant content of 2 mass% or less. It is disclosed that the agent composition has excellent detergency in washing clothes and the like, and is excellent in both foaming and rinsing properties.

JP 2011-246585 A JP-A-5-209198 JP 2011-89107 A Japanese Patent Application Laid-Open No. 2011-213992

  In the cleaning composition for clothing, in addition to having an excellent detergency, it is desired to have excellent rinsing properties such as bubbles quickly disappearing after rinsing after washing. Furthermore, in recent years, there has been an increasing interest in odors of clothing after washing, and it is also desirable to have excellent deodorizing effects that remove odors from clothing, and excellent deodorizing effects that do not generate odors such as fresh odor from washed clothing. It is.

  The present invention provides a liquid detergent composition for clothing that maintains good detergency, is excellent in rinsing properties, and has an excellent deodorizing effect on clothing.

The present invention
(A) Non-soap anionic surfactant [hereinafter referred to as component (a)] 5 mass% or more and 50 mass% or less (b) Compound selected from fatty acid and fatty acid salt [hereinafter referred to as component (b)],
(C) Alkaline agent (hereinafter referred to as (c) component),
(D) a nonionic surfactant represented by the following general formula (1) (hereinafter referred to as component (d)), and
A liquid detergent composition containing water,
As component (a), (a-1) alkylbenzene sulfonate [hereinafter referred to as component (a-1)], (a-2) alkyl sulfate (hereinafter referred to as component (a-2)), and (a) -3) containing one or more non-soap anionic surfactants selected from polyoxyalkylene alkyl ether sulfates (hereinafter referred to as component (a-3)),
The mass ratio between the mass of the component (a-1), the mass of the component (a-2), and the mass of the component (a) is [(a-1) component + (a-2) component] / (a Component) 0.5 or more and 1 or less,
The mass ratio of the mass of the component (a-3) to the mass of the component (a) is (a-3) component / (a) component, and is 0.2 or less, and
The mass ratio of the mass of the component (a-1) to the mass of the component (a-2) is (a-1) component / (a-2) component, and is 0.25 or more and 9 or less.
The present invention relates to a liquid cleaning composition for clothing.
_{^{R 1 O - [(C 2}} H 4 O) m / (AO) n] H (1)
[Wherein, R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 18 or more and 60 or less, and n is a number of 0 or more and 5 or less. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]

  ADVANTAGE OF THE INVENTION According to this invention, the favorable cleaning power is maintained, the rinse property is excellent, and the liquid detergent composition for clothing excellent in the deodorizing effect with respect to clothing is provided.

<(A) component>
The component (a) of the present invention is a non-soap anionic surfactant, and (a-1) an alkylbenzene sulfonate [component (a-1)], (a-2) an alkyl sulfate [(a-2 ) Component] and (a-3) polyoxyalkylene alkyl ether sulfate [component (a-3)] containing at least one non-soap anionic surfactant under predetermined conditions.

[(A-1) component]
The alkylbenzene sulfonate of the component (a-1) is not limited, but an alkylbenzene sulfonate having an alkyl group having 8 or more, 10 or more, and 20 or less, and 15 or less carbon atoms is preferable. . Moreover, the alkyl group which (a-1) component has has a preferable 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, component (c), a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, alkanolamine, carbonate, or the like can be used.

[(A-2) component]
The component (a-2) of the present invention is an alkyl sulfate, and the alkyl group preferably has 10 or more carbon atoms, more preferably 12 or more, and 16 or less. That is, the component (a-2) is preferably an alkyl sulfate having an alkyl group having 10 or more carbon atoms, 12 or more carbon atoms, and 16 or less carbon atoms.

  The component (a-2) is preferably an alkyl sulfate in which the proportion of linear alkyl groups having 12 to 16 carbon atoms in all alkyl groups is 50% by mass or more. From the viewpoint of reducing the environmental burden by using reproducible raw materials, the proportion of linear alkyl groups in all alkyl groups is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, 99% by mass or more is particularly preferable, and 100% by mass, that is, the component (a-2) is most preferably a linear alkyl sulfate.

  Examples of the salt constituting the component (a-2) 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 safety, an alkali metal salt is preferable, and sodium is more preferable.

[(A-3) component]
The polyoxyalkylene alkyl ether sulfate salt of the component (a-3) is not limited, but is, for example, an alkyl group having 10 or more carbon atoms, further 12 or more, 20 or less, and further 14 or less, preferably Is an alkyl group derived from a linear primary alcohol or linear secondary alcohol having 10 or more, further 12 or more, and 20 or less, or 14 or less, or a carbon number of 10 or more, further 12 or more, and 20 or less, Further, it has an alkyl group derived from 14 or less branched alcohols, and the average number of added moles of alkyleneoxy group is 0 or more, more than 0, further 0.5 or more, further 1 or more, 5 or less, further 4 or less, Furthermore, the thing of 3 or less is mentioned. The component (a-3) includes those containing an ethyleneoxy group as an alkyleneoxy group, but may contain a propyleneoxy group in an average addition mole number range of 0.2 to 2 mol. The salt is preferably an alkali metal salt, more preferably a salt selected from a sodium salt and a potassium salt, and still more preferably a sodium salt. In the present invention, the component (a-3) is a component that may be contained after satisfying a predetermined condition.

[Other components (a)]
The component (a) other than the component (a-1), the component (a-2) and the component (a-3) is selected from paraffin sulfonate, α-sulfo fatty acid alkyl ester salt, and α-olefin sulfonate. Non-soap anionic surfactants.

<(B) component>
The component (b) of the present invention is a compound selected from fatty acids and fatty acid salts. The component (b) is not limited, but as the component (b), the fatty acid having 8 or more carbon atoms, 10 or more carbon atoms, 44 or less carbon atoms, 28 or less carbon atoms, and 18 or less carbon atoms and the fatty acid. And a compound selected from the salts of: Examples thereof include those having a linear or branched alkyl group having 8 or more carbon atoms, 10 or more carbon atoms, 44 or less carbon atoms, 28 or less carbon atoms, and 18 or less carbon atoms.

  The component (b) 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. Accordingly, the component (b) is preferably a compound selected from saturated fatty acids and saturated fatty acid salts.

  Specific examples of the component (b) include lauric acid or a salt thereof, myristic acid or a salt thereof, lauric acid, a mixture of fatty acids derived from coconut rich in myristic acid or a salt thereof, and the like. From the viewpoint of foamability and rinsing properties, it is preferable to include one or more compounds selected from lauric acid and salts thereof, and myristic acid and salts thereof, and further include one or more compounds selected from myristic acid and salts thereof. Is more preferable.

  The fatty acid salt of the component (b) 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, the fatty acid which is an acid type compound may be added to the composition and neutralized with an alkali in the system, or after neutralization in advance and added to the composition May be. For neutralizing the fatty acid, component (c), a strong base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonium hydroxide, alkanolamine, carbonate or the like can be used.

As the component (b), a fatty acid having 12 to 14 carbon atoms (hereinafter referred to as _C12-14 fatty acid) and a fatty acid having 16 to 18 carbon atoms (hereinafter referred to as _C16-18 fatty acid) are contained. This is preferable in view of the stability of the composition, such as low-temperature storage stability, as well as excellent detergency, foamability and rinsing properties.

(B) When the components as comprising a C _{12 to 14} fatty acids and C _16-18 fatty acids, the weight ratio of C _16-18 fatty acid to C _{12 to 14} fatty acids, i.e., the C _16-18 fatty acid / C _{12 to 14} fatty acids From the viewpoint of improving low-temperature storage stability, the mass ratio is preferably 1/99 or more, more preferably 4/96 or more, further 8/92 or more, further 12/88 or more, and more preferably 18/82 or more. Is 60/40 or less, further 50/50 or less, and further 40/60 or less.

_{Examples of the} C _12-14 fatty acid include compounds selected from fatty acids having a straight chain or a methyl branched chain and having 12 to 14 carbon atoms and salts thereof. As _C12-14 fatty acid, it is preferable to contain a C12 fatty acid or its salt, specifically, lauric acid or its salt. Here, notation fatty acid or salt thereof having 12 carbon atoms and C ₁₂ fatty acids. (B) preferably comprises a C ₁₂ fatty acid as a component, the proportion of C ₁₂ fatty acids based on the total amount of C _{12 to 14} fatty acids 60 mass% or more, further 80% by mass or more, further 95% by mass or less, further 100 wt% Is preferred.

Moreover, as _C16-18 fatty acid, the compound chosen from the C16-C18 fatty acid which has a linear or methyl branched chain, and its salt is mentioned. As _C16-18 fatty acid, it is preferable to contain a _C16 fatty acid or its salt, specifically, palmitic acid or its salt.

Further, containing fatty acid or salt thereof having 12 carbon atoms as a C _{12 to 14} fatty acids, and preferably contains a fatty acid or salt thereof having 16 carbon atoms as a C _16-18 fatty acids. (B) in the component, further, the ratio of the sum of the C _{12 to 14} in the total content of fatty acids and C _16-18 fatty acids, the content of the fatty acid or a salt thereof and a fatty acid or salt thereof having a carbon number of 16 to 12 carbon atoms However, it is preferably 70% by mass or more, further 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.

<(C) component>
The component (c) is an alkaline agent, and examples thereof include one or more alkaline agents selected from alkanolamines, carbonates and alkali metal hydroxides. The component (c) is preferably one or more alkali agents selected from alkanolamines and carbonates.

  The component (c) has a pKa at 25 ° C. of 8.5 or more, further 8.7 or more, further 9 or more, 10.6 or less, further 10 or less, and further 9.6 or less from the viewpoint of detergency and rinsing properties. It is preferable that

  Examples of the alkanolamine include alkanolamines having 1 to 3 carbon atoms having 2 to 4 carbon atoms. Of these, the alkanol group is preferably a hydroxyethyl group. Other than the alkanol group is a hydrogen atom, but an alkyl group having 1 to 5 carbon atoms or a methyl group can be used as the component (c).

  Examples of the alkanolamine include monoethanolamine (pKa = 9.52), N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, monoalkanolamine such as monoisopropanolamine, diethanolamine (pKa). = 8.90), dialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine, and alkanolamines such as a mixture thereof (mixture of monoalkanolamine and dialkanolamine). In the present invention, one or more alkanolamines selected from monoalkanolamines and dialkanolamines are preferable, one or more alkanolamines selected from monoethanolamine and diethanolamine are more preferable, and monoethanolamine is more preferable from the viewpoint of detergency. .

  Examples of the carbonate include one or more compounds selected from the group consisting of an alkali metal hydrogen carbonate, an alkali metal carbonate, and an alkali metal sesquicarbonate. As the carbonate, an alkali metal salt such as a sodium salt is desirable, and sodium bicarbonate is preferable from the viewpoint of suppressing the salt strength of the system.

  Examples of the component (c) include one or more alkali agents selected from alkanolamines, carbonates and alkali metal hydroxides having 1 to 3 carbon atoms having 2 to 4 carbon atoms.

  In the liquid detergent composition of the present invention, as a component (c), alkanolamine and carbonate can be used in combination to improve detergency and storage stability. Therefore, it is preferable to contain alkanolamine and carbonate as the component (c).

  The component (c) may be used for neutralizing the components (a) and (b) described above. From the viewpoint of detergency and low irritation to the hand skin, it is desirable that the pH buffering ability of the liquid detergent composition of the present invention is expressed well in the pH range described below. For that purpose, the component (c) Of these, for example, it is desirable to combine compounds having a pKa at 25 ° C. in the range of 8.0 to 10.6.

  As the component (c), an alkali metal hydroxide, specifically, a compound selected from sodium hydroxide, potassium hydroxide and lithium hydroxide can be used. Ammonium hydroxide or the like can also be used. Further, the component (c) can function as a component for neutralizing the component (a) and the component (b). In addition, it is preferable to use alkali metal hydroxides, such as sodium hydroxide, in aqueous solution at the time of preparation of a composition.

<(D) component>
The component (d) of the present invention is a nonionic surfactant represented by the following general formula (1).
_{^{R 1 O - [(C 2}} H 4 O) m / (AO) n] H (1)
[Wherein, R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 18 or more and 60 or less, and n is a number of 0 or more and 5 or less. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]

In the general formula (1) of the component (d), R ¹ is a hydrocarbon group having 8 or more and 22 or less carbon atoms, a hydrocarbon group having 10 or more and 18 or less, further 16 or less, and further 14 or less. Is preferred. R ¹ is preferably a chain hydrocarbon group, and more preferably a linear hydrocarbon group. The hydrocarbon group for R ¹ is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ¹ is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. In the present invention, the carbon atom of R ¹ 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 ¹ bonded to the oxygen atom of R ¹ —O— in the general formula (1) is the first carbon atom is superior in the detergency than the compound having the second carbon atom. In particular, R ¹ is preferably a linear alkyl group having a first carbon atom.

  The method for obtaining the compound of the general formula (1) is not particularly limited, but an addition reaction of ethylene oxide with an alcohol having 8 to 22 carbon atoms, or an alkylene having 3 to 5 carbon atoms with ethylene oxide. It can be obtained by addition reaction of oxide.

M in the general formula (1) is the average added mole number of ethyleneoxy groups, and the lower limit value of m is 18 or more, and further 20 or more from the viewpoint of rinsing properties and cleaning performance. Furthermore, it may be 22 or more, 26 or more, or 30 or more. The upper limit is preferably 45 or less, more preferably 35 or less, from the viewpoint of ease of production. In the general formula (1), n is the average number of moles of alkyleneoxy group having 3 to 5 carbon atoms, and the lower limit is 0 or more, preferably 1 or more from the viewpoint of cleaning performance, and the upper limit. Is 5 or less, preferably 4 or less, more preferably 3 or less.
Furthermore, the lower limit of the total of m and n in the general formula (1) is preferably 18 or more, and more preferably 20 or more from the viewpoint of rinsing properties and cleaning performance. Furthermore, it may be 22 or more, 26 or more, or 30 or more. The upper limit is preferably 45 or less, and more preferably 35 or less, from the viewpoint of ease of production.

  In the general formula (1), the alkyleneoxy group which is AO has a methyl branched structure, an ethyl branched structure or a propyl branched structure in the case of addition reaction of alkylene oxide. AO is preferably a propyleneoxy group (hereinafter sometimes referred to as PO) obtained by addition reaction of propylene oxide.

By the way, in the case of a structure in which AO is present at a position close to R ¹ O—, since AO is a hydrophobic group, the structure is similar to a structure in which a chain hydrocarbon group as R ¹ is extended. The tendency to increase is shown. In the general formula (1), the component (d) of the present invention is such that the proportion of the compound that is R ¹ —O—C ₂ H ₄ O— is 75 mol% or more in the compound constituting the component (d). Furthermore, it is preferably 80 mol% or more (the upper limit is 100 mol% or less).

Furthermore, the component (d) has a ratio of —C ₂ H ₄ O—H at the terminal after satisfying the above-mentioned condition of R ¹ —O—C ₂ H ₄ O— in the general formula (1). Higher ones are preferred because the fiber adsorbability is lower than when the terminal is -AO-H of an alkyleneoxy group having 3 to 5 carbon atoms of the hydrophobic group. 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). The ratio of R ¹ —O—C ₂ H ₄ O— or —C ₂ H ₄ O—H can be determined by quantitative measurement using C ¹³ -NMR.

<Liquid cleaning composition>
The liquid cleaning composition of this invention contains (a) component 5 mass% or more and 50 mass% or less. From the viewpoint of deodorizing effect and detergency, the component (a) is preferably contained in the composition in an amount of 7% by mass or more, more preferably 9% by mass or more, and 40% by mass from the viewpoint of rinsing properties and product stability. % Or less, preferably 30% by mass or less, and more preferably 20% by mass or less. In the present invention, the component (a) calculates mass% and mass ratio based on the amount in terms of sodium salt.

  The liquid detergent composition of the present invention preferably contains (b) component in an amount of 0.4% by mass or more, further 0.6% by mass or more, and further 0.8% by mass or more from the viewpoint of rinsing properties. Further, from the viewpoint of foaming properties, it is preferable to contain 5% by mass or less, further 4% by mass or less, further 3% by mass or less, and further 2.5% by mass or less. In addition, in this invention, (b) component shall calculate mass% and mass ratio based on the quantity of sodium salt conversion.

  The liquid detergent composition of the present invention preferably contains (c) component in an amount of 1% by mass or more, further 1.5% by mass or more, and 6% by mass or less, and further 3% by mass or less from the viewpoint of cleaning performance. . Among the components (c), for the alkanolamine, the content in the composition is preferably 3% by mass or less from the viewpoint of the masking effect of the amine odor. Among the components (c), regarding the carbonate, from the viewpoint of product stability, the content in the composition is preferably 3% by mass or less, and more preferably 2.5% by mass or less.

The liquid detergent composition of the present invention preferably contains (d) component in an amount of 0.5% by mass or more, further 1.0% by mass or more, and further 1.5% by mass or more from the viewpoint of detergency. Further, from the viewpoint of rinsing properties, it is preferable to contain 5.0% by mass or less, further 3.0% by mass or less, and further 2.5% by mass or less.
The content of each component is selected within a range that satisfies the following mass ratio.

  In the liquid detergent composition of the present invention, the mass ratio of the mass of the component (a-1) to the mass of the component (a-2) and the mass of the component (a) is [(a-1). Component + (a-2) component] / (a) component, which is 0.5 or more and 1 or less. From the viewpoint of the deodorizing effect, the mass ratio of [(a-1) component + (a-2) component] / (a) component is 0.6 or more, further 0.7 or more, further 0.8 or more, and It is preferably 0.9 or more, more preferably 0.95 or more.

  In the liquid detergent composition of the present invention, the mass ratio of the mass of the component (a-3) to the mass of the component (a) is (a-3) component / (a) component and is 0.2 or less. . The mass ratio of component (a-3) / component (a) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0 from the viewpoint of the deodorizing effect.

  In the liquid detergent composition of the present invention, the mass ratio of the mass of the component (a-1) to the mass of the component (a-2) is (a-1) component / (a-2) component, and 25 or more and 9 or less. The mass ratio of (a-1) component / (a-2) component is 0.4 or more, further 0.45 or more, further 0.5 or more, and further 0.7 from the viewpoint of deodorizing effect and product stability. As described above, it is further preferably 0.9 or more, and more preferably 1 or more. In addition, the mass ratio of the component (a-1) / (a-2) is 6 or less, further 4 or less, further 2 or less, and further 1.5 or less from the viewpoint of the deodorizing effect and the detergency. preferable.

  In the liquid detergent composition of the present invention, the mass ratio of the mass of the component (a) to the mass of the component (d) and the mass of the component (b) is [(a) component + (d) component] / The component (b) is preferably 4 or more and 50 or less. The mass ratio of [component (a) + component (d)] / (b) is 6 or more, further 8 or more, further 10 or more, further 12 or more, and further 14 or more from the viewpoint of foaming during washing. Is preferred. The mass ratio is preferably 50 or less, more preferably 40 or less, further 30 or less, and further 25 or less from the viewpoint of rinsing properties.

  In the liquid detergent composition of the present invention, the water content is 100% by mass in the entire composition, and is 30% by mass or more, further 40% by mass or more, and further 50% by mass in the composition. The above is preferable, and 90% by mass or less, further 85% by mass or less, and further 80% by mass or less are preferable.

  The liquid detergent composition of the present invention may contain a surfactant other than the component (a), the component (b), and the component (d) as a component (f) as long as the effects of the present invention are not impaired. it can. In the present invention, the proportion of 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.

  (F) Although it does not limit as a component, Amine oxide or betaine etc. are mentioned. 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), a foam booster selected from amine oxide and betaine, especially a foam booster selected from amine oxide, is 5% by mass or less, more preferably 3% by mass or less in the composition in order not to impair the rinsing properties. Further, it is preferably 1.5% by mass or less, more preferably 0.5% by mass or less.

  Examples of the amine oxide include a monovalent alkyl group having a long chain length of 8 or more carbon atoms, 12 or more carbon atoms, 18 or less carbon atoms, and 14 or less carbon atoms, and an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. Long chain alkylamine oxides can be mentioned. 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. Among these, the content in the composition of the foam booster selected from the betaines is preferably 1.5% by mass or less, more preferably 1% by mass or less, further 0.5% by mass or less, and further preferably 0.3% by mass or less.

  Surfactants that can be used as the component (f) include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers [other than the component (d)], polyoxyalkylene alkyl phenyl ethers, and sucrose. Nonionic surfactants selected from fatty acid esters, sorbitan fatty acid esters, fatty acid alkanolamides, and alkyl glycosides can be mentioned. In addition, a cationic surfactant selected from mono- or dialkylamines and polyoxyethylene adducts thereof, and mono- or di-long-chain alkyl quaternary ammonium salts may be mentioned.

  The liquid detergent composition of the present invention preferably has a pH measured at 25 ° C. described in JIS K3362: 2008 8.3, preferably 9 or more, from the viewpoint of detergency, particularly application detergency and mildness to hand skin. More preferably, it is 9.3 or more, more preferably 9.5 or more. On the other hand, it is preferably 11 or less, more preferably 10.5 or less, more preferably 10.2 or less, and even more preferably 10 or less. The pH can be adjusted according to the type and amount of the component to be blended in the composition, and in particular, the acid type compound of the alkylbenzene sulfonate, the component (b) and the component (c) and the amount of the component. It may be adjusted using an acid agent such as hydrochloric acid (for example, 6N-HCl), citric acid, paratoluenesulfonic acid (PTS), paracumenesulfonic acid (PCS).

The liquid detergent composition of the present invention is 200 times as much as the liquid detergent composition with water of alkalinity = 65CaCO ₃ mg / l, pH 7.15, from the viewpoint of quick defoaming and washing performance, and gentleness to the hand skin. The pH of the diluted water dilution measured at 25 ° C. described in JIS K3362: 2008 8.3 is preferably 8.5 or more, more preferably 8.7 or more, still more preferably 8.9 or more, and even more preferably. It is 9 or more, preferably 10.5 or less, more preferably 10.1 or less, still more preferably 9.7 or less, and still more preferably 9.5 or less. The component (c) of the present invention is an alkaline agent having a pKa suitable for imparting such properties, and by blending them in combination, such properties can be imparted to the composition.

  The measurement method of the alkalinity of the water used for preparation of the said water dilution is shown below (Hereinafter, unless otherwise specified, the alkalinity of this invention says what was measured by this method).

Take 100 ml of test water in a 200 ml beaker and add 0.15 ml of bromocresol green-methyl red / ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) as an indicator. When there is residual chlorine in the test water, a sodium thiosulfate solution (0.3 w / v%) is added to 100 ml of the test water in advance to remove the residual chlorine. The solution is titrated with 10 mmol / l sulfuric acid with gentle stirring until the color of the solution changes from blue to reddish purple. The alkalinity is calculated by the following formula.
Alkalinity (CaCO ₃ mg / l) = a × 10
Here, a: 10 mmol / l sulfuric acid (ml) required for titration
When the color change due to the indicator is not clear, such as a colored sample, a pH meter is used instead of the indicator, and the amount of 10 mmol / l sulfuric acid (ml) required until the pH value is 4.8 is defined as a.

In addition, the liquid detergent composition of the present invention has a water dilution obtained by diluting the liquid detergent composition 200-fold with water having an alkalinity = 65CaCO ₃ mg / l, pH 7.15 from the viewpoint of quick defoaming. When 0.5 g of normal hydrochloric acid is added per liter of the water dilution, the pH measured at 25 ° C. described in JIS K3362: 2008 8.3 is 8.5 or higher, further 8.8 or higher, and further 9 or higher. Further, it is preferably 9.2 or more, and on the other hand, 11 or less, further 10 or less, and more preferably 9.5 or less. The component (c) of the present invention is an alkaline agent having a pKa suitable for imparting such properties, and by blending them in combination, such properties can be imparted to the composition. The reason for using hydrochloric acid is that it assumes acidic stains such as sweat and sebum.

  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. The content of the chelating agent in the composition is 0.001% by mass or more, further 0.01% by mass or more, further 0.03% by mass or more, or 10% by mass or less, and further 3% by mass or less. Furthermore, it is preferable that it is 1 mass% or less.

  In addition, for the purpose of improving the solution stability and transparency of the cleaning composition, a water-miscible organic solvent [hereinafter referred to as component (g)] may be contained. 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 0.1% by mass or more, further 0.3% by mass or more, further 0.5% by mass or more, and further 1% from the viewpoint of improving solution stability and transparency. It is not less than 2% by mass or more, 1.5% by mass or more, or not more than 40% by mass, further not more than 20% by mass, further not more than 10% by mass, and further not more than 5% by mass. Is preferred.

  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 as a viscosity modifier and a gelation inhibitor for the composition. 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, (g5) aromatic ethers, and more preferably (g4). Alkyl ethers. Furthermore, diethylene glycol monobutyl ether is preferred. The component (g) is effective for adjusting 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 Agent and dispersant, preferably polyacrylic acid, polymaleic acid or a salt thereof, more preferably polyacrylic acid or a salt thereof (content is preferably 0.1% by mass or more, more preferably 0.5% by mass in the composition) % Or more, further 1% by weight or more, and 10% by weight or less, further 5% by weight or less, and further 3% by weight or less)
(Ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate and 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, sodium bisulfite, etc. (Ix) Solubilizers (x) such as paratoluene sulfonic acid, cumene sulfonic acid, metaxylene sulfonic acid, benzoate (also effective as a preservative), weight average molecular weight of 200 or more and 400 or less Polyalkylene glycol-based antigelling polymers such as polyethylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or more and 2,000 or less (xi) Paraffins such as octane, decane, dodecane, tridecane, olefins such as decene, dodecene Water-immiscible organic solvents such as benzene, alkyl halides 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) Antifoaming agents such as dyes, fragrances, antibacterial preservatives, and silicones

  Although the manufacturing method of the liquid detergent composition of this invention is not specifically limited, For example, about the alkylbenzenesulfonate of (a) component, the alkylbenzenesulfonate used as the salt is used for a raw material. It can also be produced using acid-type alkylbenzene sulfonic acid as a raw material. In the latter case, for example, an alkylbenzene sulfonic acid is added to a basic compounding raw material containing water (eg, a basic aqueous solution), or an alkylbenzene sulfonic acid is added to a compounding raw material containing water (eg, an aqueous solution), and then an alkali is added. Such as adding an agent to form a salt in the composition.

  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 a washing water containing the liquid detergent composition of the present invention into contact with an object to be washed such as a fabric. The washing water can be contacted by dipping, coating, spraying, or the like. When the contact time is long, the cleaning effect is high, and when the contact time is 5 minutes or more and 15 minutes or less, a better effect is obtained. In addition, the liquid detergent composition of the present invention is directly applied to the soiled part and left for 5 to 15 minutes, and then washed with water containing the liquid detergent composition of the present invention for hand washing. Then, a higher effect can be obtained.

  As the washing water in the hand-washing washing method, the composition of the present invention or a water dilution of the composition (for example, an aqueous solution) is used. The water used here is generally tap water, and tap water in each country including Japan usually has alkalinity (buffer capacity). However, even when the liquid detergent composition of the present invention is diluted with tap water having alkalinity, the pH is 8 or more, preferably 8.5 or more, 10.5 or less exceeding the buffer capacity of the tap water. Therefore, excellent cleaning performance as designed is achieved. The mass of the washing water with respect to the mass of the object to be cleaned such as a fabric is preferably 2 times or more, further 3 times or more, further 5 times or more, 100 times or less, further 50 times or less, and further 25 times or less. 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.

  The hand-washing washing method of the present invention preferably includes a step of rinsing the article to be washed after hand washing with water. After hand washing such as rubbing, the object to be washed such as cloth is taken out from the washing water, squeezed to drain the water, or drained with a dehydrator, and dipped 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 the rinsing water with respect to the fabric is preferably 2 times or more, further 5 times or more, further 10 times or more, preferably 1,000 times or less, further 500 times or less, based on the total amount of rinsing water used for rinsing. Furthermore, it is 100 times or less. 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, foam generated at the time of washing does not disappear, so it is generally required 5 times or more, but in the present invention, it is rinsed 3 times or less. The rinsing can be completed with very little rinsing water, eliminating the need for wasteful use of water.

  In the liquid cleaning composition of the present invention, at least one of the hardness of the water used for the preparation of the cleaning water and the hardness of the rinsing water is 1 ° DH or higher, more preferably 2 ° DH or higher, from the viewpoint of cleaning power and rinsing properties. Further, it may be 3 ° DH or more, further 4 ° DH or more, further 6 ° DH or more, further 8 ° DH or more, further 10 ° DH or less, 50 ° DH or less, further 40 ° DH or less, and further 30 It is preferably at least DH and more preferably at most 20 DH.

Embodiments of the present invention are exemplified below.
<1>
(A) Non-soap anionic surfactant [hereinafter referred to as component (a)] 5 mass% or more and 50 mass% or less (b) Compound selected from fatty acid and fatty acid salt [hereinafter referred to as component (b)],
(C) Alkaline agent (hereinafter referred to as (c) component),
(D) a nonionic surfactant represented by the following general formula (1) (hereinafter referred to as component (d)), and
A liquid detergent composition containing water,
As component (a), (a-1) alkylbenzene sulfonate [hereinafter referred to as component (a-1)], (a-2) alkyl sulfate (hereinafter referred to as component (a-2)), and (a) -3) containing one or more non-soap anionic surfactants selected from polyoxyalkylene alkyl ether sulfates (hereinafter referred to as component (a-3)),
The mass ratio between the mass of the component (a-1), the mass of the component (a-2), and the mass of the component (a) is [(a-1) component + (a-2) component] / (a Component) 0.5 or more and 1 or less,
The mass ratio of the mass of the component (a-3) to the mass of the component (a) is (a-3) component / (a) component, and is 0.2 or less, and
The mass ratio of the mass of the component (a-1) to the mass of the component (a-2) is (a-1) component / (a-2) component, and is 0.25 or more and 9 or less.
Liquid detergent composition for clothing.
_{^{R 1 O - [(C 2}} H 4 O) m / (AO) n] H (1)
[Wherein, R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 18 or more and 60 or less, and n is a number of 0 or more and 5 or less. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded randomly or in blocks. ]

<2>
(A-1) The liquid detergent composition for clothing according to the above <1>, wherein the component is an alkylbenzene sulfonate having an alkyl group having 8 or more, 10 or more, and 20 or less, and 15 or less carbon atoms. .

<3>
(A-2) The liquid cleaning composition for clothing according to the above <1> or <2>, wherein the component is an alkyl sulfate having an alkyl group having 10 or more, 12 or more, and 16 or less carbon atoms.

<4>
The component (a-3) is an alkyl group having 10 or more, 12 or more, 20 or less, or 14 or less carbon atoms, preferably 10 or more, more 12 or more, 20 or less, or 14 or less. It has an alkyl group derived from a chain primary alcohol or a linear secondary alcohol, or an alkyl group derived from a branched alcohol having 10 or more, further 12 or less, and 20 or less, and further 14 or less carbon atoms. <1> to <<, wherein the polyoxyalkylene alkyl ether sulfate has a number of 0 or more, more than 0, further 0.5 or more, 1 or more, 5 or less, 4 or less, or 3 or less. 3> Liquid detergent composition for clothes given in any 1 paragraph.

<5>
The component (a) other than the component (a-1), the component (a-2), and the component (a-3) is selected from paraffin sulfonate, α-sulfo fatty acid alkyl ester salt, and α-olefin sulfonate. The liquid detergent composition for clothing according to any one of <1> to <4>, which is a non-soap anionic surfactant.

<6>
The component (b) is selected from fatty acids having a straight chain or branched chain alkyl group having 8 or more, 10 or more, 44 or less, 28 or less, and 18 or less carbon atoms, and salts of the fatty acids. The liquid cleaning composition for clothing according to any one of <1> to <5>, which is a compound.

<7>
(B) As a component, C14 or more and 14 or less fatty acid (henceforth _C12-14 fatty acid) and _C16 or more and 18 or less fatty acid (henceforth _C16-18 fatty acid) are included, The liquid cleaning composition for clothing according to any one of <1> to <6>.

<8>
The mass ratio of C _16-18 fatty acid / C _12-14 fatty acid is 1/99 or more, further 4/96 or more, further 8/92 or more, further 12/88 or more, further 18/82 or more, and preferably Is a liquid detergent composition for clothes according to the above <7>, which is 60/40 or less, further 50/50 or less, and further 40/60 or less.

<9>
The liquid detergent composition for clothing according to <7> or <8>, wherein the C _12-14 fatty acid is a fatty acid having 12 carbon atoms or a salt thereof.

<10>
The liquid detergent composition for clothing according to any one of <7> to <9>, wherein the C _16-18 fatty acid is a fatty acid having 16 carbon atoms or a salt thereof.

<11>
(B) in the component, further, the ratio of the sum of the C _{12 to 14} in the total content of fatty acids and C _16-18 fatty acids, the content of the fatty acid or a salt thereof and a fatty acid or salt thereof having a carbon number of 16 to 12 carbon atoms Is 70% by mass or more, further 80% by mass or more, further 90% by mass or more, further 95% by mass or more, and 100% by mass or less, and further 100% by mass, <7> to <10> The liquid cleaning composition for clothing according to any one of the above.

<12>
(C) The liquid cleaning composition for clothing according to any one of <1> to <11>, wherein the component is one or more alkali agents selected from alkanolamines and carbonates.

<13>
<C> The component <c> is one or more alkali agents selected from alkanolamines, carbonates and alkali metal hydroxides having 1 or more and 3 or less alkanol groups having 2 to 4 carbon atoms. The liquid cleaning composition for clothing according to any one of> to <12>.

<14>
The pKa at 25 ° C. of the component (c) is 8.5 or more, further 8.7 or more, further 9 or more, 10.6 or less, further 10 or less, and further 9.6 or less. <13> The liquid cleaning composition for clothes according to any one of the above.

<15>
The liquid detergent composition for clothing according to any one of <12> to <14>, wherein the alkanolamine is at least one selected from monoalkanolamines and dialkanolamines.

<16>
The liquid washing for clothing according to any one of the above <12> to <15>, wherein the carbonate is one or more compounds selected from the group consisting of alkali metal hydrogencarbonate, alkali metal carbonate, and alkali metal sesquicarbonate. Agent composition.

<17>
(C) The liquid cleaning composition for clothing according to any one of <1> to <16>, which contains alkanolamine and carbonate as components.

<18>
Component (d) is a nonionic surface activity of a hydrocarbon group in which R ¹ in the general formula (1) has 8 or more carbon atoms, 10 or more carbon atoms, and 22 or less, further 18 or less, further 16 or less, and further 14 or less. The liquid cleaning composition for clothing according to any one of <1> to <17>, wherein the composition is an agent.

<19>
Any one of the above <1> to <18>, wherein the component (d) is a nonionic surfactant having m in the general formula (1) of 18 or more, 20 or more, 45 or less, and 35 or less The liquid detergent composition for clothes as described.

<20>
<1> to <19, wherein the component (a) is contained in the composition at 7% by mass or more, further 9% by mass or more, and 40% by mass or less, further 30% by mass or less, and further 20% by mass or less. > The liquid detergent composition for clothes in any one of>.

<21>
The component (b) in the composition is 0.4% by mass or more, further 0.6% by mass or more, further 0.8% by mass or more, 5% by mass or less, further 4% by mass or less, and further 3%. The liquid detergent composition for clothes according to any one of <1> to <20>, further containing 2.5% by mass or less, and further 2.5% by mass or less.

<22>
(C) Liquid washing | cleaning for clothes in any one of said <1>-<21> containing 1 mass% or more, further 1.5 mass% or more, 5 mass% or less, and further 3 mass% or less Agent composition.

<23>
The component (d) is 0.5 mass% or more, further 1.0 mass% or more, further 1.5 mass% or more, 5.0 mass% or less, further 3.0 mass% or less, and further 2. The liquid detergent composition for clothing according to any one of <1> to <22>, which is contained in 5% by mass or less.

<24>
The mass ratio of [(a-1) component + (a-2) component] / (a) component is 0.6 or more, further 0.7 or more, further 0.8 or more, further 0.9 or more, and further 0 The liquid cleaning composition for clothing according to any one of <1> to <23>, which is .95 or more.

<25>
The liquid detergent for clothing according to any one of <1> to <24>, wherein the mass ratio of (a-3) component / (a) component is 0.1 or less, further 0.05 or less, and further 0. Composition.

<26>
The mass ratio of (a-1) component / (a-2) component is 0.4 or more, further 0.45 or more, further 0.5 or more, further 0.7 or more, further 0.9 or more, further 1 or more. And the liquid cleaning composition for clothes in any one of said <1>-<25> which is 6 or less, further 4 or less, further 2 or less, and also 1.5 or less.

<27>
The mass ratio of the mass of the component (a) and the mass of the component (d) to the mass of the component (b) [(a) component + (d) component] / (b) component is 4 or more, further 6 or more The clothing according to any one of <1> to <26>, further 8 or more, 10 or more, 12 or more, 14 or more, 50 or less, 40 or less, 30 or less, or 25 or less. Liquid detergent composition.

<28>
The amount of water is 100% by mass in the entire composition. Further, in the composition, 30% by mass or more, further 40% by mass or more, further 50% by mass or more, and 90% by mass or less, The liquid detergent composition for clothing according to any one of <1> to <27>, further 85% by mass or less, and further 80% by mass or less.

<29>
(F) As a component, the content of a foam booster selected from amine oxide and betaine, especially a foam booster selected from amine oxide is 5% by mass or less, further 3% by mass or less, and further 1.5% in the composition. The liquid detergent composition for clothing according to any one of <1> to <28>, wherein the composition is 0.5% by mass or less, and further 0.5% by mass or less.

<30>
The pH measured at 25 ° C. described in JIS K3362: 2008 8.3 is preferably 9 or more, more preferably 9.3 or more, more preferably 9.5 or more, and preferably 11 or less, more preferably 10. The liquid detergent composition for clothing according to any one of <1> to <29>, which is 5 or less, more preferably 10.2 or less, and even more preferably 10 or less.

<31>
Alkalinity = 65 CaCO ₃ mg / l, pH measured at 25 ° C. described in JIS K3362: 2008 8.3 of water dilution diluted 200 times with water of pH 7.15, preferably 8.5 or more, more preferably 8.7 or more, more preferably 8.9 or more, even more preferably 9 or more, and preferably 10.5 or less, more preferably 10.1 or less, still more preferably 9.7 or less, and even more preferably 9 The liquid cleaning composition for clothing according to any one of <1> to <30>, which is 0.5 or less.

<32>
(G) As a component, a water-miscible organic solvent that dissolves 50 g or more in 1 liter of ion-exchanged water at 25 ° C. In addition, 1% by mass or more, 1.5% by mass or more, further 2% by mass or more, and 40% by mass or less, further 20% by mass or less, further 10% by mass or less, and further 5% by mass or less, The liquid cleaning composition for clothing according to any one of <1> to <31>.

<33>
The liquid detergent composition for clothing excellent in deodorizing / deodorizing effect according to any one of <1> to <32>.

<34>
The hand-washing washing method which wash | cleans the to-be-washed | cleaned material which contacted the washing water containing the liquid cleaning composition for clothing as described in any one of said <1>-<33>.

<35>
The hand-washing method according to <34>, wherein the contact time is 5 minutes or more and 15 minutes or less.

<36>
It includes a process of rinsing the object to be cleaned after hand washing with water, and at least one of the hardness of the water used to prepare the cleaning water and the hardness of the rinse water is 1 ° DH or more, 2 ° DH or more, and 3 ° DH or more Further, 4 ° DH or more, further 6 ° DH or more, further 8 ° DH or more, further 10 ° DH or less, 50 ° DH or less, further 40 ° DH or less, further 30 ° DH or more, further 20 ° DH or less. The hand-washing washing method according to <34> or <35>.

  The liquid detergent composition shown in Table 1 was prepared, and the deodorizing effect, cleaning power, and rinsing property were evaluated by the following methods. The results are shown in Table 1. In addition, the compounding component in a table | surface is the following. Further, in the table, “appropriate amount” of NaOH is an amount necessary for setting the pH of the composition to the value in the table.

<Blending ingredients>
LAS-Na: sodium laurylbenzenesulfonate, Neoperex G-15 (manufactured by Kao Corporation)
AS-Na: sodium lauryl sulfate, Emar 10G (manufactured by Kao Corporation)
AES-Na (EO = 2): polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate ester, Emar 270J (manufactured by Kao Corporation)
・ C12FA: LUNAC L-98 (manufactured by Kao Corporation)
・ C16FA: LUNAC P-95 (manufactured by Kao Corporation)
NaHCO ₃ : manufactured by Wako Pure Chemical Industries, Ltd. EO nonion (1): polyoxyethylene alkyl ether obtained by adding an average of 20 moles of ethylene oxide to a primary alcohol having a linear alkyl group having 10 to 14 carbon atoms. Nonion (2): A block in which an average of 9 mol of ethylene oxide is added to a primary alcohol having a linear alkyl group having 10 to 14 carbon atoms, then an average of 2 mol of propylene oxide is added, and an average of 9 mol of ethylene oxide is added. Polymerized polyoxyalkylene alkyl ether / EO nonion (3): polyoxyethylene alkyl ether / EO nonion (4) obtained by adding an average of 35 moles of ethylene oxide to a primary alcohol having a linear alkyl group having 10 to 14 carbon atoms : Primary alkyl having a linear alkyl group having 10 to 14 carbon atoms Polyoxyethylene alkyl ethers average 7 to mols of ethylene oxide to call

<Method for preparing underwear for evaluation>
A commercial underwear 2.5kg [Gunze (YG1614 round neck L size 100% cotton)] was washed with a washing machine (Panasonic NA-F70PB1 '2008) using a water temperature of 20 ° C and 89.5mg / L of hard water in terms of calcium carbonate. Washing was repeated 5 times to remove the treatment agent. Washing conditions were 54L of water, 12 minutes of washing, two rinses, and 5 minutes of dehydration. At that time, a nonionic surfactant (a primary alcohol composed of an alkyl group having 12 carbon atoms added with an average of 6 mol of oxyethylene group), amorphous sodium silicate, and sodium carbonate 1: 1: 1. A mixture with a mass ratio of 0.5 g / L was used. Thereafter, running water was rinsed with a two-tank washing machine (manufactured by HITACHI, PS-H35L'2008) using hard water having a water temperature of 20 ° C. and 89.5 mg / L in terms of calcium carbonate. When rinsing was stopped, rinsing was performed until the foam disappeared completely, and the treatment agent and the cleaning component were removed and dried by natural drying, and used as an underwear for evaluation.

<Evaluation>
(1) Deodorizing effect One test towel piece (6 cm x 6 cm square) was prepared for each towel from the used towels (material: cotton) collected one by one from three households (total of three towels) A piece was prepared). Using the liquid detergent composition shown in the table, the three towel pieces were washed (targotometer 85 rpm, 10 minutes, concentration of liquid detergent composition 1% by mass, rinse 3 minutes twice), and then 30 ° C. And dried in a constant temperature room with a humidity of 70% for 12 hours. The average of 10 towel panelists (10 men and women in their 20s and 30s) who judged their odors based on the following criteria for 3 towel pieces dried in a temperature-controlled room. By the point, the deodorizing effect of the liquid detergent composition was evaluated. The average score is shown in the table.
* Odor criteria 0: Odorless 1: Slightly smelled but not worrisome 2: Smelled 3: Remarkably smelled 4: Strongly smelled

(2) 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 having the following composition (mass% in artificial dirt is 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 9.31 mass% palmitic acid, heptadecane 0.44% by mass of acid, 1.6% by mass of stearic acid, 1.91% by mass of oleic acid, 13.33% by mass of trimyristin, 5.22% by mass of n-hexadecyl palmitate, and 6.66% by mass of squalene. Used in quantity)
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%
Adjustment oil 1% by mass of lauric acid, 7.1% by mass of myristic acid, 5.3% by mass of pentadecanoic acid, 14.2% by mass of palmitic acid, 1% by mass of heptadecanoic acid, 3.6% by mass of stearic acid, 17 of oleic acid 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.

[Cleaning conditions]
2 g of the liquid detergent composition was converted into calcium carbonate (179 mg / L, alkalinity 65 CaCO ₃ mg / l, pH 7.15 hard water [calcium chloride (CaCl ₂ · 2H ₂ O) 1.57 g and magnesium sulfate (MgSO ₄ · 6H ₂ O) 1.45 g of sodium bicarbonate and 1.6 g of baking soda to make 10 L, adjusted with hydrochloric acid, dissolved in 1 L of Ca / Mg = 6/4 (molar ratio)], and the above artificial contamination Four sheets of cloth were put and washed with a targotometer under the following conditions.
Washing time 10 minutes Water temperature 20 ° C

The raw cloth before contamination and the reflectance at 550 nm before and after washing were measured with a colorimetric color difference meter (Nippon Denshoku Co., Ltd., Z-300A), and the washing rate (%) was determined by the following equation (four sheets) Use the average cleaning rate).
Washing rate (%) = 100 × [(reflectance after washing−reflectivity before washing) / (reflectance of base fabric−reflectivity before washing)]
The determination of the cleaning power was performed by comparing the cleaning rate of the liquid cleaning composition in Table 1 with the cleaning rate of Comparative Example 1. And it evaluated as follows. Here, the cleaning rate of Comparative Example 1 was 34%.
I: The cleaning rate is 6% or more higher than that of Comparative Example 1.
II: The cleaning rate is 2% or more and less than 6% higher than Comparative Example 1.
III: The cleaning rate is less than 2% higher than that of Comparative Example 1, or the cleaning rate is equal to or lower than that of Comparative Example 1.

(3) Rinse evaluation In a model circular washbasin (cylindrical acrylic container with a bottom diameter of 25 cm and a height of 15 cm), a water temperature of 20 ° C. and 179 mg / L in terms of calcium carbonate (this hard water has a German hardness of 10 ° DH) corresponding), alkalinity 65CaCO ₃ mg / l, hard water pH7.15 [calcium chloride _{(CaCl 2 · 2H 2 O)} 1.57g magnesium sulphate _{(MgSO 4 · 6H 2 O)} 1.45g and sodium bicarbonate 1.6g Ion exchange water is added to make 10 L, and adjusted with hydrochloric acid, Ca / Mg = 6/4 (molar ratio)] 3 L is injected. Thereto, 20 g of the liquid detergent composition is added and dissolved. Next, heat the adjustment oil used in the detergency evaluation (60 ° C.), and add 3 g of spoil (φ: 2 mm) to the neck so that it becomes 1 g (about 0.33 g per sheet). The evaluation underwear dripped in is used, and left for 15 minutes in a state of being completely immersed in the cleaning liquid. After leaving for 15 minutes, it is washed 50 times per piece of undergarment (converted to 1 in 1 reciprocation (about 1 second) while rubbing the cloths together). Thereafter, the underwear is taken out and squeezed so that the moisture content of the underwear is about 100 to 140% of the underwear.

A new model circular washbasin (cylindrical acrylic container with a bottom diameter of 25 cm and a height of 15 cm), a water temperature of 20 ° C., 179 mg / L in terms of calcium carbonate, alkalinity 65CaCO ₃ mg / l (hard water is from Germany) 5L of hard water (corresponding to 10 ° DH in hardness) and pH 7.15 hard water (prepared in the same manner as used in the evaluation of the detergency) is injected, and three pieces of the underwear for evaluation are squeezed as described above. After rinsing the undergarment in the water, lift the loose undergarment one by one from the bath, lifting it up from the bath to the height of about 5 cm above the washbasin until the entire clothing is removed. Return to the bath again. After rinsing by such up-and-down movement is repeated 10 times for each undergarment, the undergarment is squeezed 10 cm above the basin so that the moisture content of the undergarment is about 100 to 140% of the undergarment. Rinse the three underwears and observe the level of the rinse water immediately after the dehydration is finished. This is one evaluation. Further, new rinse water is added to the dehydrated underwear, and this evaluation is repeated two more times (repeatedly using the same three underwear for one liquid detergent composition). The rinsability was evaluated at the average score.
* Point criteria 6: Bubbles with a height of 1 cm or more remain on the entire liquid surface 5: Bubbles remain 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

Claims (8)

(A) Non-soap anionic surfactant [hereinafter referred to as component (a)] 5 mass% or more and 50 mass% or less (b) Compound selected from fatty acid and fatty acid salt [hereinafter referred to as component (b)],
(C) Alkaline agent (hereinafter referred to as (c) component),
(D) a nonionic surfactant represented by the following general formula (1) (hereinafter referred to as component (d)), and
A liquid detergent composition containing water,
(A) As component of component (a-1) alkylbenzene sulfonate [hereinafter referred to as component (a-1)], (a-2) straight chain having 12 to 16 carbon atoms in all alkyl groups An alkyl sulfate having an alkyl group ratio of 50% by mass or more (hereinafter referred to as component (a-2)), and (a-3) a polyoxyalkylene alkyl ether sulfate having an average added mole number of alkyleneoxy groups of greater than zero. Including one or more non-soap anionic surfactants selected from salts [hereinafter referred to as component (a-3)] ,
The mass ratio of the ingredients (a-1) as a mass and a blending component in component (a-2) component of the total mass and the mass of the (a) component, [(a-1) component + (a -2) component] / (a) component, 0.5 or more and 1 or less,
The mass ratio of the mass of the component (a-3) as the blending component and the mass of the component (a) is (a-3) component / (a) component, and is 0.2 or less, and
The mass ratio of the mass of the component (a-2) as a mass and a blending component in component (a-1) as a blending component, the component (a-1) / (a-2) in component than 0.25 , 9 or less
Liquid detergent composition for clothing.
^{_{R 1 O - [(C 2}} H 4 O) m / (AO) n] H (1)
[Wherein, R ¹ is a linear hydrocarbon group having 8 to 22 carbon atoms, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 18 or more and 60 or less, and n is a number of 0 or more and 5 or less. “/” Indicates that the C ₂ H ₄ O group and the AO group may be bonded to either random or block. ]   The mass ratio of the mass of the component (a) to the mass of the component (d) and the mass of the component (b) is [(a) component + (d) component] / (b) component, 4 or more, 50 The liquid detergent composition for clothes according to claim 1 which is the following.   The detergent composition for liquid clothing according to claim 1 or 2, wherein the component (b) is a compound selected from fatty acids having 10 to 18 carbon atoms and salts of the fatty acids.   (B) Liquid detergent composition for clothes of any one of Claims 1-3 which contains a C12-C14 fatty acid and a C16-C18 fatty acid as a component. .   The liquid cleaning composition for clothing according to any one of claims 1 to 4, wherein the component (c) is one or more alkali agents selected from alkanolamines and carbonates.   The liquid detergent composition for clothes excellent in the deodorizing and deodorizing effect of any one of Claims 1-5. (A) Non-soap anionic surfactant [hereinafter referred to as component (a)] 5 mass% or more and 50 mass% or less
(B) a compound selected from fatty acids and fatty acid salts [hereinafter referred to as component (b)],
(C) Alkaline agent (hereinafter referred to as (c) component),
(D) a nonionic surfactant represented by the following general formula (1) (hereinafter referred to as component (d)), and
water
A method for producing a liquid detergent composition comprising
(A) as component (a-1) alkylbenzene sulfonate [hereinafter referred to as component (a-1)], (a-2) straight chain alkyl group having 12 to 16 carbon atoms in all alkyl groups Alkyl sulfate having a proportion of 50% by mass or more (hereinafter referred to as component (a-2)), and (a-3) polyoxyalkylene alkyl ether sulfate having an average added mole number of alkyleneoxy groups greater than 0 1 or more non-soap anionic surfactant selected from (a-3) component]
The mass ratio between the mass of the component (a-1), the mass of the component (a-2), and the mass of the component (a) is [(a-1) component + (a-2) component] / (a ) Component, 0.5 or more, 1 or less,
The mass ratio of the mass of the component (a-3) to the mass of the component (a) is (a-3) component / (a) component, 0.2 or less, and
The mass ratio of the mass of the component (a-1) to the mass of the component (a-2) is (a-1) component / (a-2) component, and is 0.25 or more and 9 or less,
(A-1) component, (a-2) component, and (a-3) component are blended so that
A method for producing a liquid detergent composition for clothing.
R ¹ O-[(C ₂ H ₄ O) _m / (AO) _n ] H (1)
[In the formula, R ¹ Is a linear hydrocarbon group having 8 to 22 carbon atoms, and AO is an alkyleneoxy group having 3 to 5 carbon atoms. m and n are average added mole numbers, m is a number of 18 or more and 60 or less, and n is a number of 0 or more and 5 or less. “/” Is C ₂ H ₄ It shows that O group and AO group may be bonded to either random or block. ] The manufacturing method of the liquid cleaning composition for garments of Claim 7 which manufactures the liquid cleaning composition for garments of any one of Claims 1-6.