WO2014050710A1 - Liquid detergent - Google Patents

Abstract

A liquid detergent contains a component (A): 30% by mass or more of a nonionic surfactant, a component (B): one or more anionic surfactants selected from a sulfonate and a sulfuric acid ester salt, and a component (C): an organic solvent having a specific structure. The ratio of component (C) to component (A) by mass is 0.04 to 0.5.

Description

Liquid cleaning agent

The present invention relates to a liquid cleaning agent.
This application claims priority based on Japanese Patent Application No. 2012-210777 for which it applied to Japan on September 25, 2012, and uses the content here.

Conventionally, as liquid detergents for textile products and the like, those using a nonionic surfactant as a main cleaning component, those using a combination of a nonionic surfactant and an anionic surfactant, and the like have been widely used.
In recent years, with the aim of saving resources and reducing the environmental burden (reducing the amount of waste), the size of detergent containers has been reduced, and as a result, the concentration of liquid detergents (higher concentrations of surfactants) has been increased. ) Is required.
As the liquid detergent is concentrated, the liquid stability of the liquid detergent is lowered, and a film is formed or gelation is likely to occur. If the liquid cleaning agent forms a film or gels, it becomes difficult to pour the liquid cleaning agent from the container, or the dispersibility in water and the permeability to the object to be washed are impaired. Conventionally, attempts have been made to prevent liquid detergent film formation and gelation.

For example, a liquid detergent composition containing a specific alkylene oxide adduct, an amidoamine compound, and an anionic surfactant has been proposed (for example, Patent Document 1).
In addition, a technique for suppressing the formation of a film or gelation of a liquid detergent by adding ethanol, butyl carbitol, or the like is generally known.

JP 2009-144002 A

However, when a liquid detergent containing ethanol is poured out of a container and left in an open system, for example, film formation or gelation is likely to occur due to evaporation of moisture and solvent due to drying. Since butyl carbitol has a peculiar odor, the odor is liable to adhere to an object to be washed or the odor of a flavoring agent blended in a liquid detergent is likely to be impaired. For this reason, it is still difficult to put them into practical use by adding them to a liquid detergent to suppress film formation and gelation.

The present invention has been made based on such a background, and an object of the present invention is to provide a liquid cleaning agent that can satisfactorily prevent film formation and gelation and has good odor.

The liquid detergent of the present invention has the following aspects (1) to (12).
(1) (A) component: 30% by mass or more of a nonionic surfactant, (B) component: one or more anionic surfactants selected from sulfonates or sulfates, and (C) components: An organic solvent represented by the formula (I), and a mass ratio represented by the component (C) / the component (A) is 0.04 to 0.5.

(In the formula (I), R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group.)

(2) In the liquid cleaning agent of (1), in the component (C), two or three of R ¹ to R ³ are hydrogen atoms.

(3) In the liquid cleaning agent of (1) or (2), in the component (C), ^{one of the} R ¹ to R ³ is an alkyl group.

(4) In the liquid cleaning agent of (3), the component (C) has 1 or 2 carbon atoms in the alkyl group.

(5) In the liquid cleaning agent according to any one of (1) to (4), in the component (C), R ⁴ is a hydrogen atom.

(6) In the liquid detergent according to any one of (1) to (5), the component (C) is 3-methoxybutanol or a derivative thereof.

(7) In the liquid cleaning agent of (6), the component (C) is 3-methoxy-3-methylbutanol.

(8) In the liquid detergent according to any one of (1) to (6), the content of the component (C) in the liquid detergent is 1 to 20% by mass with respect to the total mass of the liquid detergent. It is.

(9) In the liquid detergent according to any one of (1) to (8), the component (B) is a linear alkylbenzene sulfonic acid or a salt thereof, an alkane sulfonate, a polyoxyethylene alkyl ether sulfate ester salt, And an α-olefin sulfonate.

(10) In the liquid detergent according to any one of (1) to (9), the component (A) is a compound represented by the following general formula (a1).
R ¹¹ -X-[(EO) _s / (PO) _t ] -R ¹² (a1)
(R ¹¹ : hydrocarbon group having 8 to 18 carbon atoms, X: O, COO or CONH, R ¹² : hydrogen atom, alkyl group having 1 to 6 carbon atoms or alkenyl group having 2 to 6 carbon atoms, []: repetition Structure, EO: oxyethylene group, PO: oxypropylene group, s: average number of repetitions of EO, t: average number of repetitions of PO, s = 3 to 20, t = 0 to 6)

(11) In the liquid detergent according to any one of (1) to (9), the component (A) is a compound represented by the following general formula (a2).
R ¹³ —O — [(EO) _p / (PO) _q ] — (EO) _r —H (a2)
(R ¹³ : hydrocarbon group having 8 to 18 carbon atoms, []: repeating structure, EO: oxyethylene group, PO: oxypropylene group, p: average repeating number of EO, q: average repeating number of PO, r: EO average number of repetitions, p> 1, r> 1, 0 <q ≦ 3, p + r = 10 to 20)

According to the liquid cleaning agent of the present invention, film formation and gelation can be prevented satisfactorily and the odor is good.

Hereinafter, the present invention will be specifically described with reference to embodiments.

(Liquid cleaning agent)
The liquid detergent according to the present embodiment includes (A) component: a nonionic surfactant, (B) component: one or more anionic surfactants selected from sulfonates or sulfate esters, and (C) component. : Contains a specific organic solvent.

The viscosity of the liquid detergent of the present embodiment is not particularly limited, but is preferably 30 to 300 mPa · s, for example. When the viscosity is not more than the above upper limit value, the permeability to the textile product or the like that is the object to be washed can be increased during the application cleaning.
The above-mentioned viscosity value is a value measured at 25 ° C. Even if the viscosity is outside the range specified in the present specification, it is included in the scope of the present invention if the viscosity is within the range specified in the present specification when corrected to the viscosity at 25 ° C.
The viscosity of the liquid detergent can be measured using a capillary tube viscometer or a rotary viscometer, etc., and particularly preferably measured using a rotary viscometer. It is more preferable to use and measure. In the present embodiment, as an example, a value measured by a B-type viscometer (manufactured by TOKIMEC) (measurement conditions: rotor No. 2, rotation speed 30 rpm, value after 10 rotations) can be used.

The pH of the liquid detergent of this embodiment is preferably 4-9. When the pH of the liquid cleaning agent is within the range of 4 to 9, the coating cleaning power is further increased. The pH of the liquid detergent is more preferably 6 to 9, and within this range, there is an advantage that the liquid appearance stability is good.
The above-mentioned pH value is a value measured at 25 ° C. Even a pH outside the range specified in the present specification is included in the scope of the present invention if the pH is within the range specified in the present specification when corrected to a pH at 25 ° C.
The pH of the liquid detergent can be measured appropriately using a test paper, a test solution, an electrical pH measuring device (such as a pH meter) or other measuring means. In the present embodiment, as an example, a value measured by a pH meter (HM-30G, manufactured by Toa DKK Corporation) or the like can be used.

<(A) component: nonionic surfactant>
The component (A) is a nonionic surfactant. The component (A) is used for imparting detergency to the liquid detergent.
Nonionic surfactants (sometimes called nonionic surfactants, nonionic surfactants, nonionic surfactants, nonionic surfactants or nonionic surfactants) are dissolved in water. It refers to a surfactant that does not exhibit ionic properties. Nonionic surfactants used for component (A) include, for example, fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids, higher fatty acid alkyl esters or alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers , Fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or its alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkylamine oxide, alkenylamine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester, N- Examples include alkyl polyhydroxy fatty acid amides and alkyl glucosides.

Especially, (A) component is represented by the polyoxyalkylene type nonionic surfactant (henceforth (a1) component) represented by the general formula (a1) mentioned later or the general formula (a2) mentioned later. A polyoxyalkylene type nonionic surfactant (hereinafter sometimes referred to as component (a2)) is preferred. These (A) components may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the component (A) in the liquid detergent of this embodiment is 30% by mass or more, preferably 30 to 70% by mass with respect to the total mass of the liquid detergent. When the content of the component (A) is 30% by mass or more of the lower limit with respect to the total mass of the liquid detergent, sufficient detergency can be exhibited. That is, in this embodiment, since the component (B) and the component (C) described later are contained, film formation and gelation hardly occur even if the concentration of the component (A) is increased. (A) It can be set as 30 mass% or more of component, and it can be set as a liquid cleaning agent with the high cleaning power per liquid quantity. Moreover, by forming the component (A) in the liquid detergent to be 70% by mass or less, film formation and gelation can be made more difficult to occur.

Furthermore, the content of the component (A) is more preferably 30 to 60% by mass with respect to the total mass of the liquid detergent, and there is an advantage that sufficient detergency can be exhibited within this range. The content of the component (A) is particularly preferably 40 to 50% by mass with respect to the total mass of the liquid detergent, and there is an advantage that film formation and gelation can be prevented within this range.

<(A1) component>
In the present embodiment, as the component (a1), a compound represented by the following chemical formula can be used.
R ¹¹ -X-[(EO) _s / (PO) _t ] -R ¹² (a1)

(In the formula (a1), R ¹¹ is a hydrocarbon group having 8 to 18 carbon atoms. X is O, COO or CONH. R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or An alkenyl group having 2 to 6 carbon atoms, [] represents a repeating structure, and [(EO) _s / (PO) _t ] represents a structure of the compound of the component (a1) in which EO or PO is enclosed in []. It shows that it has a repeating structure, wherein EO represents an oxyethylene group, PO represents an oxypropylene group, and each compound may have only one of EO and PO in the repeating structure, If each compound has a mixture of EO and PO, EO and PO may be arranged in any order, and s is the average of EO Represents the number of repetitions and is selected from a number from 3 to 20. t is the average repetition of PO And is selected from a number of 0 to 6. Here, the average number of repetitions varies in the number of EO or PO contained in each molecule (the number of repetitions) when the above-mentioned compound is produced. For convenience, a value obtained by averaging the number of repetitions for each molecule is referred to as an average number of repetitions, and the average number of repetitions is obtained by averaging the molar ratio of EO or PO added to 1 mol of the component (a2) at the time of synthesis. Although it can be almost regarded as the value of the number of repetitions, to obtain the average number of repetitions strictly, the molecular weight distribution is obtained by gas chromatography etc. for a sample with a fixed number of moles, and the average number of repetitions estimated from the molecular weight is obtained. May be.)

In the formula (a1), the carbon number of R ¹¹ is preferably 10 to 18 from the viewpoint of improving detergency.
R ¹¹ is preferably an alkyl group or an alkenyl group, and may be linear or branched.
Examples of R ¹¹ include raw materials such as primary or secondary higher alcohols, higher fatty acids or higher fatty acid amides, and alkyl groups or alkenyl groups derived therefrom. Here, higher alcohols, higher fatty acids, higher fatty acid amides, and the like are higher alcohols, higher fatty acids, higher fatty acid amides, etc. having a carbon chain having 5 or more carbon atoms as a guide.

When R ¹² is an alkyl group, R ¹² preferably has 1 to 3 carbon atoms.
When R ¹² is an alkenyl group, R ¹² preferably has 2 to 3 carbon atoms.

X is preferably O or COO.
In the formula (a1), when X is O, the component (A) is an alkyl ether type nonionic surfactant.
When X is O, R ¹¹ is preferably an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms. By using these for the compound represented by (a1), the cleaning power of the liquid detergent is increased. When X is O, R ¹¹ may have an unsaturated bond. When X is O, R ¹² is preferably a hydrogen atom.

In the formula (a1), when X is COO, the component (A) is a fatty acid ester type nonionic surfactant. When X is COO, R ¹¹ preferably has 9 to 18 carbon atoms. By using these for the compound represented by (a1), the cleaning power of the liquid detergent is increased. Further, the carbon number of R ¹¹ is more preferably 11 to 18, and there is an advantage that the appearance stability is good in this range. R ¹¹ may have an unsaturated bond. When X is COO, R ¹² is preferably an alkyl group having 1 to 3 carbon atoms.

In the formula (a1), s is a number from 3 to 20. When s exceeds 20, the HLB value (affinity between the water layer and the hydrophobic layer of the surfactant) of the liquid detergent becomes too high, and the detergency tends to decrease. If s is less than 3, the raw material odor of the component (A) itself tends to deteriorate. Further, s is preferably 5-18.
t is a number from 0 to 6. When t exceeds 6, the storage stability of the liquid detergent at a high temperature tends to decrease. Further, t is preferably a number from 0 to 3.

EO and PO may be mixedly arranged, and (EO) _s / (PO) _t may be arranged in a so-called random manner in which EO and PO do not have regularity in the arrangement. Further, EO and PO may be arranged in a so-called block shape in which a fixed number of blocks are arranged and the blocks are arranged.

In the component (a1), the addition mole number distribution of EO or PO is not particularly limited, and is likely to vary depending on the reaction method in producing the component (a1). Here, the number of added moles indicates the number of moles of an added group (group to be added to the compound, here EO or PO) with respect to 1 mole of the raw material. The average number of moles added is the average of the number of moles added per molecule of the compound. When adding an additional group during the production of the compound, the value of the ratio of the number of moles of the added group to 1 mole of the compound is regarded as the average average number of moles added. It's okay. When a precise value is required for the average number of moles added, the molecular weight of each molecule contained in a compound with a fixed number of moles is measured by chromatography, and the number of moles added per molecule is estimated from the molecular weight. Find on average. The added mole number distribution is a distribution of the added mole number for each molecule contained in a certain amount of the compound. In the present embodiment, the following narrow ratio is used as an index. The molecular weight of each contained molecule is measured by chromatography or the like within a certain number of moles of the compound, and the number of moles added is estimated. “Nlmax” is the number of moles of the additional group of the molecule present in the largest amount in the total compound. The total mass (nlmax-1 to 1) of the molecules having the addition group number of moles of addition (nlmax-1), nlmax, and (nlmax + 1) is determined. The ratio of “nlmax−1 to 1” with respect to the mass of all molecules in the compound is defined as the narrow ratio.
The addition mole number distribution of EO or PO is, for example, a raw material (primary or secondary higher alcohol, higher fatty acid, higher fatty acid) using ethylene oxide or propylene oxide using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. When added to a fatty acid amide or the like, the distribution tends to be relatively wide.
The added mole number distribution of EO or PO includes metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ and Mn ²⁺ described in JP-B-6-15038. When ethylene oxide or propylene oxide is added to a raw material using a specific alkoxylation catalyst such as added magnesium oxide, the distribution tends to be relatively narrow.
The liquid detergent has a narrow distribution of added moles (narrow), that is, a larger narrow ratio, the more stable the chemical characteristics of the liquid detergent and the stronger the detergency for a specific compound. On the other hand, when the added mole number distribution is broad (broad), that is, the narrow ratio is small, the liquid detergent contains compounds having various chemical characteristics, so that various stains can be washed. Therefore, it is preferable to design the added mole number distribution according to the purpose of the liquid detergent.

(A1) The specific example of a component is shown. Diadol (trade name, C13 (C represents the number of carbon atoms; hereinafter the same)) manufactured by Mitsubishi Chemical Co., Ltd. Neodol (trade name, a mixture of C12 and C13) manufactured by Shell, or Safol 23 (product manufactured by Sasol) Name, a mixture of C12 and C13), etc., with 12 mole equivalent or 15 mole equivalent ethylene oxide added; CO-1214 or CO-1270 (product of Procter & Gamble Co., Ltd.) Name) and the like, to which 12 moles or 15 moles of ethylene oxide is added per 1 mole of natural alcohol, etc .; And 7 mol equivalent of ethylene oxide (trade name: Lutensol TO7, BA F product); 9 mole equivalent of ethylene oxide added to 1 mole of C10 alcohol obtained by subjecting pentanol to gerbet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mole equivalent of ethylene oxide added to 1 mole of the C10 alcohol obtained (product name: Lutensol XL70, manufactured by BASF); 1 mole of C10 alcohol obtained by subjecting pentanol to the garbed reaction , 6 mol equivalent of ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 9 mol equivalent or 15 mol equivalent of ethylene oxide was added to 1 mol of secondary alcohol having 12 to 14 carbon atoms Things (Product name: Softanol 90, So Tanol 150, manufactured by Nippon Shokubai Co., Ltd .; 1 mol of palm fatty acid methyl (lauric acid / myristic acid = 8/2) added with 15 mol of ethylene oxide using an alkoxylation catalyst (polyoxyethylene) And coconut fatty acid methyl ester (EO 15 mol)).

When particularly emphasizing the viewpoint of improving the cleaning ability of the liquid detergent, it is preferable to use the component (a1) as the component (A).

<(A2) component>
In the present embodiment, as the component (a2), a compound represented by the following chemical formula can be used.
R ¹³ —O — [(EO) _p / (PO) _q ] — (EO) _r —H (a2)

(In the formula (a2), R ¹³ is a hydrocarbon group having 8 to 18 carbon atoms. [] Represents a repeating structure, and [(EO) _s / (PO) _t ] represents the compound of the component (a1)). It shows that the structure has a structure in which EO or PO is repeated in [], where EO represents an oxyethylene group, PO represents an oxypropylene group, and each compound has a structure of EO and PO in the repeating structure. If each compound has a mixture of EO and PO, the EO and PO are arranged in any order. P represents the average number of repetitions of EO in the repeating structure, q represents the average number of repeating POs in the repeating structure, r represents the average number of repeating EO outside the repeating structure, and p , Q, r are p> 1, r> 1, 0 <q ≦ 3, p + r = 10 to 20 It is a number that satisfies.

(A2) In the formula, R ¹³ is preferably an alkyl group or an alkenyl group. R ¹³ may be linear or branched.
In the formula (a2), the ratio of EO to PO is preferably 0.1 to 0.5 in terms of q / (p + r). When the ratio represented by q / (p + r) is not less than the above 0.1 value, bubbles are not excessively formed, and it is easy to optimize the bubbles. By being 0.5 or less, an appropriate viscosity can be easily obtained, and gelation can be suppressed more favorably. The ratio of EO and PO is more preferably 0.1 to 0.3.

EO and PO may be mixedly arranged, and (EO) _p / (PO) _q may be added in a so-called random form in which EO and PO do not have regularity in the arrangement. Further, EO and PO may be added in a so-called block form in which a fixed number of blocks are arranged and the blocks are arranged.

The component (a2) can be produced by a known method. For example, after adding ethylene oxide and propylene oxide in this order to an alcohol having R ¹³ derived from natural fats and oils, or after adding and mixing ethylene oxide and propylene oxide (random addition), ethylene oxide is added again. , (A2) can be produced.

By using the component (a2) as the component (A), the liquid detergent tends to have an appropriate viscosity, and the gelation can be suppressed more favorably. Moreover, foamability improves and biodegradability also becomes better.

<(B) component: one or more anionic surfactants selected from sulfonates or sulfates>
The component (B) contained in the liquid detergent of the present embodiment is one or more anionic surfactants selected from components: sulfonates or sulfates. The liquid detergent can favorably prevent film formation and gelation by containing the component (B).

Anionic surfactants (sometimes called anionic surfactants, anionic surfactants, anionic surfactants, anionic surfactants or anionic surfactants) are dissolved in water. A surfactant that becomes anionic and has an anionic hydrophilic group.

Examples of the anionic surfactant used in the component (B) include linear alkylbenzene sulfonic acid or a salt thereof; α-olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester or alkenyl ether Sulfuric acid ester salts; alkane sulfonic acid salts having alkyl groups; or α-sulfo fatty acid ester salts are preferred. The sulfuric acid or sulfo fatty acid ester salt of the above-mentioned compounds refers to those in which the sulfuric acid group or fatty acid group of these compounds forms a salt with a metal or an amine. Examples of salts in these non-soap anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
As the linear alkylbenzene sulfonic acid or a salt thereof, one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
As the α-olefin sulfonate, those having 10 to 20 carbon atoms are preferable. As the alkyl sulfate ester salt, those having an alkyl group having 10 to 20 carbon atoms are preferred.

The alkyl ether sulfate or alkenyl ether sulfate used for the component (B) is a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. You may have. Moreover, you may have an oxyethylene group or an oxypropylene group.
The alkanesulfonic acid salt preferably has an alkyl group having 10 to 20 carbon atoms, more preferably 14 to 17 carbon atoms. Among these, those in which the alkyl group is a secondary alkyl group (that is, secondary alkane sulfonate) are particularly preferable.
The α-sulfo fatty acid ester salt preferably has 10 to 20 carbon atoms in the fatty acid residue.
Among these, as the component (B), at least one compound selected from linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate is used. It is particularly preferred. In particular, when a linear alkylbenzene sulfonic acid or a salt thereof is used for the component (B), the stability is high and the odor is suppressed, but the effect of increasing the stability is particularly high. By using a polyoxyethylene alkyl ether sulfate ester salt as the component (B), the stability is high and the odor is suppressed, but the effect of suppressing the odor is particularly high.

As the component (B), other non-soap anionic surfactants other than those described above may be used. Examples of the other non-soap anionic surfactants include carboxylic acids such as alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, and acylaminocarboxylates. Type anionic surfactants; phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts or glycerin fatty acid ester monophosphoric acid ester salts Can be mentioned.
These (B) components are easily available on the market.
These (B) components may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the component (B) in the liquid detergent of this embodiment is preferably 1 to 20% by mass with respect to the total mass of the liquid detergent. When the content of the component (B) is in the range of 1 to 20% by weight, it is easier to prevent film formation and gelation of the liquid detergent, and the low temperature stability of the liquid detergent can be enhanced. The content of the component (B) is more preferably 2 to 10% by mass. Within this range, film formation, gelation prevention, and low temperature stability can be achieved at a high level. The content of component (B) is more preferably 3 to 8% by mass.

In the liquid cleaning agent of this embodiment, the mass ratio represented by the component (A) / component (B) (hereinafter sometimes referred to as A / B ratio) is preferably 3 to 50. If the A / B ratio is 3 or more, film formation or gelation can be prevented more favorably. If the A / B ratio is 50 or less, the odor of the article to be washed is less likely to be impaired. The A / B ratio is more preferably 5-20. More preferably, the A / B ratio is 7-15.

<(C) component: specific organic solvent>
(C) component contained in the liquid cleaning agent of this embodiment is the organic solvent represented by the following general formula (I). By containing the component (C), the liquid cleaning agent of this embodiment can satisfactorily prevent film formation and gelation and can improve odor.

Describing in more detail, the component (C) has low volatility. For this reason, the liquid detergent contains the component (C), so that it is difficult to cause film formation or gelation even when left in an open system. In addition, by containing the component (C) in the liquid detergent, it is difficult to impair the flavor of the flavoring agent blended in the liquid detergent. Furthermore, by containing the component (C) in the liquid cleaning agent, it is difficult for the odor of the component (C) to remain in the article to be cleaned.

 

(In the formula (I), R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group.)

(I) In the formula, R ¹ to R ³ are all hydrogen atoms, or one is an alkyl group and the other two are hydrogen atoms, that is, two of R ¹ to R ³ Or three (two or more, at least two) are preferably hydrogen atoms. If two or ^three of R ¹ to R ³ are hydrogen atoms, film formation and gelation can be better prevented even when left in an open system.
When any of R ¹ to R ³ is an alkyl group, the alkyl group preferably has 1 to 2 carbon atoms, and more preferably 1 carbon atom. If the carbon number of R ¹ to R ³ is within the above range, film formation and gelation can be prevented more favorably even when left in an open system.
R ⁴ is preferably a hydrogen atom from the viewpoint of better preventing film formation and gelation even when left in an open system.

Component (C) includes 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol, 3- In the formula (I), such as methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol or 3-methoxy-1-propylbutanol Wherein R ⁴ is a hydrogen atom; 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3-methoxy- 2-methylbutyl acetate, 3-methoxy-2-ethylbutyl acetate, 3-methyl R ⁴ in the formula (I) such as toxi-2-propylbutyl acetate, 3-methoxy-1-methylbutyl acetate, 3-methoxy-1-ethylbutyl acetate, 3-methoxy-1-propylbutylacetate is an acetyl group And the like.

Among them, the component (C) includes 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol or 3-methoxy-3-methylbutyl acetate Is preferred. Furthermore, as the component (C), 3-methoxy-3-methylbutanol is more preferable.
These (C) components may be used alone or in combination of two or more.

The content of the component (C) in the liquid detergent of this embodiment is preferably 1 to 20% by mass with respect to the total mass of the liquid detergent. If content of (C) component is 1 mass% or more of the above, it is easier to prevent film formation and gelation of the liquid detergent, and the low temperature stability of the liquid detergent can be enhanced. When the content of the component (C) is 20% by mass or less, the odor of the component (C) is less likely to migrate to the object to be washed, and the odor of the liquid cleaning agent itself is less likely to be impaired. The content of component (C) is more preferably 2 to 15% by mass. The content of component (C) is more preferably 3 to 10% by mass.
The component (C) is preferably used in combination with a water-miscible organic solvent (C ′) other than the component (C), and more preferably used in combination with ethanol. When (C) + (C ′) <5, (C) / (C ′) is preferably 4 or more. When 5 ≦ (C) + (C ′), (C) / (C ′) is preferably 0.5 to 10, more preferably 1 to 4. By being in the said range, an odor and film formation prevention become further favorable.

In the liquid detergent of the present embodiment, the mass ratio represented by the component (C) / component (A) (hereinafter also referred to as C / A ratio) is 0.04 to 0.5. If the C / A ratio is less than 0.04, film formation or gelation of the liquid detergent cannot be prevented satisfactorily, and if it exceeds 0.5, the odor of the liquid detergent tends to be impaired. The C / A ratio is preferably 0.04 to 0.3. The C / A ratio is more preferably 0.04 to 0.18.

The liquid cleaning agent of this embodiment contains water as a solvent for dispersing the above-described components (A) to (C) and optional components described later. The content of water in the liquid detergent is, for example, preferably 10 to 70% by mass and more preferably 20 to 40% by mass with respect to the total mass of the liquid detergent.

<Optional component>
The liquid detergent of the present embodiment can contain optional components other than the components (A) to (C) as necessary. Optional components include surfactants (arbitrary surfactants) other than components (A) to (B), thickeners, solubilizers, sequestering agents, antioxidants, texture improvers, fluorescent whitening agents. , Anti-staining agents, enzymes, flavoring agents, coloring agents, emulsifying agents, extracts, pH adjusting agents, pearling agents or soil release agents.

Examples of the optional surfactant include a cationic surfactant, an amphoteric surfactant, and a higher fatty acid salt.
A cationic surfactant (also called a cationic surfactant, a cationic surfactant, a cationic surfactant, a cationic surfactant or a cationic surfactant) is dissolved in water. It is a surfactant that becomes cationic and has a cationic hydrophilic group. Examples of the cationic surfactant include cationic surfactants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. In the liquid detergent, the content of the cationic surfactant is preferably 0.1 to 8.0% by mass with respect to the total mass of the liquid detergent.
An amphoteric surfactant can have a positive or negative charge as a whole depending on the pH in water when dissolved in water, and examples thereof include those having both anionic and cationic hydrophilic groups. Examples of amphoteric surfactants include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant. Is mentioned. In the liquid detergent, the content of the amphoteric surfactant is preferably 0.05 to 5.0% by mass with respect to the total mass of the liquid detergent.
Examples of higher fatty acid salts include higher fatty acid salts having 10 to 20 carbon atoms. In the liquid detergent, the content of the higher fatty acid salt is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent. If the content of the higher fatty acid salt is 0.01% by mass or more, the defoaming property at the time of cleaning can be enhanced, and if the content exceeds 5% by mass, film formation or gelation of the liquid detergent tends to occur. There is a tendency.

Examples of the thinning agent or solubilizer include toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate, xylene sulfonate, cumene sulfonate, or substituted Alternatively, unsubstituted naphthalene sulfonate can be mentioned. Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
A thinning agent or a solubilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
In the liquid detergent of the present embodiment, the content of the viscosity reducing agent or solubilizer is preferably 0.01 to 15% by mass with respect to the total mass of the liquid detergent. If it is in the said range, the film formation of a liquid cleaning agent can be prevented more.

Examples of the alkali agent include alkanolamine. Examples of the alkanolamine include monoethanolamine, diethanolamine, or triethanolamine. An alkali agent may be used individually by 1 type, and 2 or more types may be used in combination.
In the liquid cleaning agent of this embodiment, the content of the alkaline agent is preferably 0.5 to 5% by mass with respect to the total mass of the liquid cleaning agent, for example.

Examples of the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid.
A metal ion scavenger may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the metal ion scavenger in the liquid detergent of this embodiment is preferably 0.1 to 20% by mass with respect to the total mass of the liquid detergent.

Although it does not specifically limit as antioxidant, A phenolic antioxidant is preferable from the viewpoint of favorable detergency and liquid stability. As the phenolic antioxidant, dibutylhydroxytoluene, butylhydroxyanisole, 2,2′-methylenebis (4-methyl-6-t-butylphenol) or dl-α-tocopherol is more preferable, and dibutylhydroxytoluene, dl-α -Tocopherol is particularly preferred.
An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the antioxidant in the liquid detergent of this embodiment is preferably 0.01 to 2% by mass with respect to the total mass of the liquid detergent.

Examples of the texture improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
The content of the texture improving agent in the liquid detergent of this embodiment is preferably 0 to 5% by mass with respect to the total mass of the liquid detergent.

Examples of the fluorescent whitening agent include a distyrylbiphenyl type whitening agent.
The fluorescent brightening agent may be used alone or in combination of two or more.
The content of the optical brightener in the liquid detergent of this embodiment is preferably 0 to 1% by mass with respect to the total mass of the liquid detergent.

Examples of the recontamination preventive agent include polyvinyl pyrrolidone and carboxymethyl cellulose.
A recontamination inhibitor may be used individually by 1 type, and 2 or more types may be used in combination.
The content of the anti-fouling agent in the liquid detergent of this embodiment is preferably 0 to 2% by mass with respect to the total mass of the liquid detergent.

Examples of the enzyme include protease, lipase, cellulase, and preparations thereof.

The flavoring agent is not particularly limited as long as it is conventionally used in liquid detergents. For example, hydrocarbon, ether, alcohol, phenol, phenol ether, aldehyde, acetal, ketal, ketone, lactone, ester Or it selects suitably from the substance selected from compounds, such as a sulfur containing type | system | group, or a natural fragrance | flavor or a synthetic fragrance | flavor. Examples thereof include perfume compositions A to D described in Tables 11 to 18 of JP-A No. 2002-146399.
The content of the flavoring agent in the liquid detergent of this embodiment is preferably 0.1 to 1% by mass with respect to the total mass of the liquid detergent.

Colorants include general-purpose dyes and pigments such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, or Turquoise P-GR (all trade names) Is mentioned.
The content of the colorant in the liquid cleaning agent of this embodiment is preferably 0.00005 to 0.005% by mass with respect to the total mass of the liquid cleaning agent.

Examples of the emulsion include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Examples of emulsion emulsions include polystyrene emulsion (trade name: Cybinol RPX-196 PE-3, solid content 40% by mass, manufactured by Syden Chemical Co., Ltd.).
The content of the emulsion in the liquid detergent of this embodiment is preferably 0.01 to 0.5% by mass with respect to the total mass of the liquid detergent.

Extracts include Inuenju, waurusushi, echinacea, koganebana, yellowfin, yellow spider, allspice, oregano, enju, chamomile, honeysuckle, clara, keigai, kei, bay geese, honoki, burdock, comfrey, ginger, walnut, ginger, ginger , Sequoia spp. , Pokeweed, cedar, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsam, hakse , Kochia, Polygonum aviculare, Jingyou, Liquidambar formosana, Adenophortriphylla, Yamabishi, cayratia japonica, licorice or St. John's wort, etc. of the plant extracts and the like.
The content of the extracts in the liquid detergent of this embodiment is preferably 0 to 0.5% by mass with respect to the total mass of the liquid detergent.

In order to set the pH of the liquid cleaning agent of this embodiment to a desired value, a pH adjusting agent may be blended. However, when the liquid cleaning agent has a desired pH only with the above-described components, the pH adjusting agent may not be used.
Examples of the pH adjuster include acidic compounds such as sulfuric acid and hydrochloric acid; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkaline compounds such as sodium hydroxide and potassium hydroxide. From the viewpoint of increasing the temporal stability of the liquid detergent, sulfuric acid, sodium hydroxide, potassium hydroxide or alkanolamine is preferable, and sulfuric acid or sodium hydroxide is more preferable.
These pH adjusters may be used alone or in combination of two or more. The content of the pH adjusting agent in the liquid detergent is appropriately selected according to the target pH.

As a modification of the liquid battlefield agent of the present embodiment, a liquid detergent that contains at least the components (A) to (C) and does not contain water may be used. In this case, the liquid detergent may be dispersed in water immediately before use, or may be dissolved in washing water when used.

(Method for producing liquid detergent)
Examples of the method for producing the liquid detergent of this embodiment include a method of dispersing the components (A) to (C) and, if necessary, optional components in a dispersion medium such as water. As a manufacturing method of a liquid detergent, the following methods are mentioned, for example. The components (B) to (C) described above are dispersed in a small amount of water. At this time, the above-mentioned optional components are dispersed in this water as necessary. After visually confirming that these components are sufficiently dispersed in water, the dispersed aqueous solution is adjusted to an arbitrary pH. To adjust the pH, the above pH adjuster may be added, or other acids, alkalis, pH buffering agents, and the like may be added. Next, the component (A) is dispersed in the aqueous solution adjusted in pH. Thereafter, the pH is further adjusted to an arbitrary pH that reaches the final pH of the liquid cleaning agent, and water is further added to obtain the liquid cleaning agent. Water is preferably added in an amount of 10 to 70% by mass relative to the total mass of the liquid detergent, and more preferably 20 to 40% by mass.

(How to use liquid detergent)
The method of using the liquid cleaning agent of the present embodiment (the cleaning method using the liquid cleaning agent of this embodiment) is the same as the method of using a general liquid cleaning agent.
For example, a method in which a liquid cleaning agent is placed in water together with the object to be cleaned and washed in a washing machine, a method in which the liquid cleaning agent is directly applied to the object to be cleaned, a liquid cleaning agent dissolved in water to form a cleaning liquid, and the cleaning liquid For example, a method of immersing the washing product. Moreover, after apply | coating a liquid cleaning agent to to-be-washed object and leaving it to stand suitably, you may wash | clean using a washing machine etc. In the case of a method in which a liquid cleaning agent is put into water together with an object to be washed and washed in a washing machine, the amount of the liquid cleaning agent relative to water varies depending on the components of the liquid cleaning agent, but as a guide, the amount of liquid cleaning liquid The cleaning effect is obtained when the cleaning agent is 0.03 to 1% by volume. The cleaning time and number of times vary depending on the amount and material of the object to be cleaned, the weight of dirt, the concentration of the liquid cleaning agent, or the concentration of the liquid cleaning agent. In the case of washing an amount to be washed so that it is immersed in water used for washing, washing for 5 to 30 minutes is preferably performed about 1 to 4 times. In the method in which the liquid detergent is dissolved in water to immerse the object to be washed, the content of the liquid detergent may be the same as that in the washing machine described above, but the liquid detergent is thicker (the content is higher). The amount of the liquid detergent is preferably 0.06 to 5% by volume with respect to the volume of water.
Although it does not specifically limit as a to-be-washed object, For example, the liquid detergent of this embodiment is preferably applicable to textiles, such as clothing, a cloth, a sheet, a curtain, or a carpet.

As described above, according to the present invention, since the component (A) is contained in an amount of 30% by mass or more with respect to the total mass of the liquid detergent, a high detergency can be exhibited in a small amount.
In addition, since the liquid detergent contains the component (B) and the component (C), film formation and gelation can be satisfactorily prevented.
Furthermore, since the liquid detergent contains the component (C), the odor is good.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

(Raw materials used)
<(A) component: nonionic surfactant>
A-1: A product obtained by adding 12 moles of ethylene oxide to 1 mole of natural alcohol (LMAO). Synthesized in Synthesis Example 1 below.

<< Synthesis Example 1 >> Synthesis of A-1 Pressure resistance of 861.2 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of 30% by mass NaOH aqueous solution with respect to the total mass of the liquid detergent The reactor was charged into a mold reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating the inside of the container at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Next, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution while stirring the reaction solution in the container. At this time, ethylene oxide was added through the blowing tube while adjusting the addition rate so that the reaction temperature in the container did not exceed 180 ° C.
After completion of the addition of ethylene oxide, the container was aged for 30 minutes at a temperature of 180 ° C. and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature in the vessel to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid is added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction is about 7, and A -1 (LMAO) was obtained.

A-2: Methyl coconut fatty acid (mixture of methyl laurate / methyl myristate = 8/2 by mass ratio) with 1 mol of ethylene oxide added using an alkoxylation catalyst (methyl ester) Ethoxylate, MEE). Synthesized in Synthesis Example 2 below.

Synthesis Example 2 Synthesis of A-2 Synthesis was performed according to the synthesis method described in Japanese Patent Application Laid-Open No. 2000-144179 (corresponding to sample D).
Alumina-magnesium hydroxide (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO.Al ₂ O ₃ .wH ₂ O was calcined at 600 ° C. for 1 hour in a nitrogen atmosphere. Thus, a calcined alumina / magnesium hydroxide (unmodified) catalyst was obtained. A 4 L autoclave was charged with 2.2 g of this calcined alumina / magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester, Catalyst reforming was performed in an autoclave. Next, after the inside of the autoclave was replaced with nitrogen, 1052 g of ethylene oxide was introduced and reacted while stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa.
The resulting reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, respectively, and the catalyst was filtered off to obtain A-2 (MEE).

A-3: Softanol 90 (trade name, manufactured by Nippon Shokubai Co., Ltd.) 9 mole equivalent of ethylene oxide added to 1 mole of secondary alcohol having 12 to 14 carbon atoms.
A-4: Lutensol XP90 (trade name, manufactured by BASF). 9 mol equivalent of ethylene oxide added to 1 mol of C10 alcohol obtained by subjecting pentanol to garvet reaction A-5: Average addition to 1 mol of C10-14 primary alcohol A block addition of ethylene oxide in order of 9 moles, propylene oxide to have an average added mole number of 2 moles, and ethylene oxide to have an average added mole number of 9 moles. (A2) In the formula, R ¹³ is a linear alkyl group having 10 to 14 carbon atoms, p = 9, q = 2, and r = 9. In the table, described as an alcohol EOPO adduct.

<(B) component: anionic surfactant>
B-1: LAS, linear alkyl (carbon number 10 to 14) benzenesulfonic acid (trade name: Raipon LH-200 (LAS-H), pure content 96% by mass, manufactured by Lion Corporation), average molecular weight 322 (liquid When producing the cleaning agent, it is neutralized with sodium hydroxide, which is a pH adjusting agent, to form a sodium salt).

B-2: AES, sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average added mole number of ethylene oxide 2). Synthesized in Synthesis Example 3 below.

AES, sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average added mole number of ethylene oxide is 2). Synthesized in Synthesis Example 3 below.
<< Synthesis Example 3 >> Synthesis of B-2 In a 4 L autoclave, Neodol 23 (trade name, C12,13 alcohol (a mixture of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms in a mass ratio of 1/1) was used as a raw alcohol. ), Branching rate 20% by mass, manufactured by Shell) 400 g and potassium hydroxide catalyst 0.8 g. The autoclave was purged with nitrogen and heated with stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining the inside of the autoclave at a temperature of 180 ° C. and a pressure of 0.3 mPa, to obtain a reaction product (alcohol ethoxylate) having an average addition mole number of ethylene oxide of 2.
280 g of the resulting alcohol ethoxylate was charged into a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 67 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropwise addition, the contents of the flask were stirred for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Further, this was neutralized with an aqueous sodium hydroxide solution to obtain B-2 (AES).
The distribution of the number of added moles of ethylene oxide of B-2 was evaluated by measuring the narrow rate of ethylene oxide. The narrow rate of ethylene oxide was determined as follows.
The number of moles of ethylene oxide adduct of the ethylene oxide adduct most present on a mass basis in all ethylene oxide adducts constituting AES is defined as “nlmax”. For the ethylene oxide adducts with the number of moles of ethylene oxide added (nlmax-1), nlmax, and (nlmax + 1), the total mass (nlmax-1 to 1) is determined. The ratio of “nlmax−1 to 1” with respect to the mass of all ethylene oxide adducts in AES is defined as the narrow ratio.
The narrow ratio of the B-2 ethylene oxide obtained was 35% by mass.

B-3: Secondary alkanesulfonic acid Na (SAS), SAS30 (trade name, manufactured by Clariant Japan KK).
B-4: Polyoxyalkylene alkyl ether sulfate monoethanolamine salt (linear alkyl having 10 to 14 carbon atoms, PO average addition mole number 1, EO average addition mole number 3)

<(C) component: specific organic solvent>
C-1: 3-methoxy-3-methylbutanol (trade name: Solfit, manufactured by Kuraray Co., Ltd.).
C-2: 3-methoxy-3-methylbutyl acetate (trade name: Solfit AC, manufactured by Kuraray Co., Ltd.).

<(C ′) component: Comparative product of component (C)>
C′-1: Ethanol (trade name: specified alcohol 95 degree synthesis, manufactured by Nippon Alcohol Sales Co., Ltd.)
C′-2: Butyl carbitol (manufactured by Nippon Emulsifier Co., Ltd.)

<PH adjuster>
Sodium hydroxide or sulfuric acid: an appropriate amount (the amount necessary for adjusting to the pH in the table). The total pH adjusting agent in the liquid detergent of each example was 0 to 3% by mass.
<Water>
Purified water: Balance (amount for making the total amount of liquid detergent 100% by mass).

<Common ingredients>
Hereinafter, “mass%” described at the end of each component is the content in the liquid detergent finally adjusted in each example.
Paratoluenesulfonic acid: PTS acid (trade name), manufactured by Kyowa Hakko Kogyo Co., Ltd .... 1% by mass.
Monoethanolamine: manufactured by Nippon Shokubai Co., Ltd. 1% by mass.
Isogo fatty acid: NOF Corporation 1 mass%.
Palmitic acid: NOF Corporation 0.1 mass%.
Flavoring agent: Fragrance composition A described in Tables 11 to 18 of JP-A-2002-146399: 0.4% by mass.
Dibutylhydroxytoluene (BHT): SUMILZER BHT-R (trade name), manufactured by Sumitomo Chemical Co., Ltd. 0.05 mass%.
Lactic acid: Pure Chemical Co., Ltd .... 1% by mass.
Coloring agent: Green No. 3, manufactured by Sakai Kasei Co., Ltd., 0.0002% by mass.
Enzyme: Coronase (trade name), manufactured by Novozyme, ... 0.6% by mass.
Citric acid: Liquid citric acid (trade name), manufactured by Yushi Kogyo Co., Ltd. 0.1 mass%.

(Evaluation methods)
<Stability>
10 g of the liquid cleaning agent of each example was placed in a plastic container (length 5 cm × width 5 cm × height 3 cm) and stored in a constant temperature and humidity chamber at 25 ° C. and 30% RH for 40 hours. The plastic container used for the test has an open top. Each of the liquid detergents was stored in a constant temperature and humidity chamber for 40 hours, and then the stability was evaluated according to the following evaluation criteria.

≪Evaluation criteria≫
A: There is no film formation or gelation, and it is uniformly transparent and fluid.
○: Dust is observed, but no film formation or gelation occurs, and fluidity is present.
Δ: No gelation and fluidity, but a film is formed on the surface.
X: Gelation occurs and fluidity is remarkably reduced.

<Odor>
Ten pieces of commercially available cotton towels (100% cotton) are put into a two-tank washing machine (trade name: CW-C30A1, manufactured by Mitsubishi Electric Corporation), and 12 liters of tap water and 8 ml of the liquid cleaning agent in each example are used in the two-tank type. I put it in the washing machine. This cotton towel was washed in the washing machine with a weak water flow, with a washing time of 10 minutes, a dehydration of 1 minute, a rinse (once for 3 minutes each) and a dehydration of 1 minute. The temperature of the tap water used was 25 ° C. This washing operation was repeated 5 times. After five washing operations (after dehydration), a cotton towel was used as a test cloth.
Separately, instead of the liquid cleaning agent in each example, using 16 mL of a 20% by weight aqueous solution of a nonionic surfactant (alcohol ethoxylate in which ethylene oxide having an average addition mole number of 15 mol is added to 1 mol of lauryl alcohol), A cotton towel subjected to the above washing operation 5 times was used as a control cloth.
Ten panelists evaluated the test cloth and the control cloth according to the following evaluation criteria. The average score of 10 panelists was evaluated, ◎ for 3.5 points or more, ◯ for 3.0 points or more and less than 3.5 points, △ for 2.5 points or more and less than 3.0 points, △, 2.5 Less than a point was set as x.

≪Evaluation criteria≫
1 point: The evaluation cloth feels an unusual odor (odor different from the fragrance) much stronger than the control cloth.
2 points: The evaluation cloth feels a different odor than the control cloth.
3 points: The evaluation fabric feels a slightly different odor than the control fabric.
4 points: The unpleasant odor of the evaluation cloth and the unpleasant odor of the control cloth are equivalent.
5 points: The control fabric feels a strange odor stronger than the evaluation fabric.

(Adjustment of Examples 1 to 21 and Comparative Examples 1 to 5)
According to the composition of Tables 1-2, in a 500 mL beaker, (B) component, (C) component (or (C ') component) and a part of water are put, and this is magnetically stirrer (made by MITAMURA KOGYO INC.). Stir. Next, PTS, monoethanolamine, and coconut fatty acid were added to the beaker, and then a pH adjuster was added to adjust the pH to 7. To this beaker, the remainder of the common components other than the enzyme was added, while stirring, water was added so that the total amount was 95% by mass, and a pH adjuster was added to adjust the pH in Tables 1 and 2. Next, an enzyme was added to the beaker, and the remainder of water was added so that the total amount was 100% by mass, thereby obtaining the liquid cleaning agent of each example.
About the obtained liquid cleaning agent, stability and odor were evaluated and the result is shown in a table | surface.
In addition, the composition in a table | surface is the pure amount conversion amount of each component.

(Examples 22 to 23)
According to the composition of Table 3, the liquid detergents of Examples 22 and 23 were obtained in the same manner as Examples 1 to 21. Table 3 also shows the C / C ′ ratio for Example 21.

 

 

In Tables 1 and 2, with respect to the odor evaluation results, the average score is described in the upper part and the evaluation is described in the lower part.
As shown in Tables 1 and 2, in Examples 1 to 21 to which the present invention was applied, the stability evaluation was “◯” or “◎”, and film formation and gelation were satisfactorily suppressed. . In addition, in Examples 1 to 21, the odor was evaluated as “◯” or “」 ”, and the off-flavor derived from the component (C) was suppressed.
On the other hand, Comparative Example 1 containing no component (B) had a stability evaluation of “Δ”, and Comparative Example 2 using ethanol instead of the component (C) had a stability evaluation of “x”. . In Comparative Example 3 using butyl carbitol instead of the component (C), the odor was evaluated as “x”. In Comparative Example 4 in which C / A was 0.02, the stability evaluation was “Δ”, and in Comparative Example 5 in which C / A ratio was 0.67, the odor evaluation was “x”.
From these results, it was found that by applying the present invention, film formation and gelation can be prevented satisfactorily and odor can be improved.

According to the liquid detergent of the present invention, film formation and gelation can be satisfactorily prevented, and the odor is good. Therefore, the liquid detergent can be widely used in households, industries, and other places where detergents are used.

Claims (11)

1. Component (A): 30% by mass or more of a nonionic surfactant, Component (B): one or more anionic surfactants selected from sulfonates and sulfates, and component (C): the following general formula (I A liquid detergent having a mass ratio represented by the component (C) / the component (A) of 0.04 to 0.5.
   

   

   
   (In the formula (I), R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group.)
2. 2. The liquid cleaning agent according to claim 1, wherein in the component (C), two or three of R ¹ to R ³ are hydrogen atoms.
3. The liquid cleaning agent according to claim 1 or 2, wherein in the component (C), ^{one of the} R ¹ to R ³ is an alkyl group.
4. The liquid cleaning agent according to claim 3, wherein the component (C) has 1 or 2 carbon atoms in the alkyl group.
5. 5. The liquid cleaning agent according to claim 1, wherein the component (C) is such that R ⁴ is a hydrogen atom.
6. 6. The liquid cleaning agent according to claim 1, wherein the component (C) is 3-methoxybutanol or a derivative thereof.
7. The liquid cleaning agent according to claim 6, wherein the component (C) is 3-methoxy-3-methylbutanol.
8. The content of the component (C) in the liquid cleaning agent is 1 to 20% by mass with respect to the total mass of the liquid cleaning agent, according to any one of claims 1 to 6. Liquid cleaning agent.
9. The component (B) is selected from at least one selected from linear alkylbenzene sulfonic acid or a salt thereof, alkane sulfonate, polyoxyethylene alkyl ether sulfate, and α-olefin sulfonate. The liquid cleaning agent according to any one of claims 1 to 8.
10. The liquid cleaning agent according to any one of claims 1 to 9, wherein the component (A) is a compound represented by the following general formula (a1).
    R ¹¹ —X — [(EO) _s / (PO) _t ] —R ¹² (a1) (R ¹¹ : hydrocarbon group having 8 to 18 carbon atoms, X: O, COO or CONH, R ¹² : Hydrogen atom, alkyl group having 1 to 6 carbon atoms or alkenyl group having 2 to 6 carbon atoms, []: repeating structure, EO: oxyethylene group, PO: oxypropylene group, s: average repeating number of EO, t: PO S = 3 to 20, t = 0 to 6)
11. The liquid cleaning agent according to claim 1, wherein the component (A) is a compound represented by the following general formula (a2).
    R ¹³ —O — [(EO) _p / (PO) _q ] — (EO) _r —H (a2)
    (R ¹³ : hydrocarbon group having 8 to 18 carbon atoms, []: repeating structure, EO: oxyethylene group, PO: oxypropylene group, p: average repeating number of EO, q: average repeating number of PO, r: EO average number of repetitions, p> 1, r> 1, 0 <q ≦ 3, p + r = 10 to 20)