KR102206771B1 - Liquid detergent - Google Patents

Abstract

(A) component: 30% by mass or more of nonionic surfactant, (B) component: at least one anionic surfactant selected from sulfonate and sulfuric ester salt, and (C) component: an organic solvent having a specific structure And the mass ratio represented by the component (C)/component (A) is 0.04 to 0.5.

Description

Liquid detergent {LIQUID DETERGENT}

The present invention relates to a liquid detergent.

This application claims priority based on patent application 2012-210777 for which it applied to Japan on September 25, 2012, and uses the content here.

Conventionally, as a liquid detergent for textile products, a nonionic surfactant as a main cleaning component, a nonionic surfactant and an anionic surfactant are used together.

In recent years, for the purpose of saving resources and reducing the environmental load (reducing the amount of waste), miniaturization of detergent containers has been pursued, and concentrating liquid detergents (higher concentration of surfactants) have been demanded.

As the liquid detergent is concentrated, the liquid stability of the liquid detergent is lowered and a film is easily formed or gelation occurs. When the liquid detergent forms a film or gelation occurs, it becomes difficult to pour the liquid detergent out of the container, or the dispersibility into water or the permeability to the object to be washed is impaired. Conventionally, attempts have been made to prevent formation of a film or gelation of a liquid detergent.

For example, a liquid detergent composition containing a specific alkylene oxide adduct, an amide amine compound, and an anionic surfactant has been proposed (for example, Patent Document 1).

In addition, techniques for suppressing film formation or gelation of a liquid detergent by adding ethanol or butylcarbitol are generally known.

Japanese Patent Application Publication No. 2009-144002

However, when a liquid detergent containing ethanol is poured out of a container and left in an open system, for example, film formation and gelation are likely to occur due to volatilization of moisture or solvent by drying. Since butylcarbitol has a peculiar odor, it is easy to adhere the odor to the object to be washed or to damage the fragrance of the flavoring agent blended in the liquid detergent. Therefore, it is difficult to put them into practical use yet to suppress film formation or gelation by adding these to a liquid detergent.

The present invention has been made on the basis of such a background, and an object thereof is to provide a liquid detergent capable of preventing film formation and gelation satisfactorily and having a good odor.

The liquid detergent of the present invention has the following forms (1) to (12).

(1) (A) component: 30 mass% or more of nonionic surfactant, (B) component: at least one anionic surfactant selected from sulfonate or sulfuric ester salt, and (C) component: the following general formula (I The organic solvent represented by) is contained, and the mass ratio represented by the said (C) component/the said (A) component is 0.04 to 0.5.

(In 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 detergent of the above (1), in the component (C), two or ^three of R ¹ to R 3 are hydrogen atoms.

(3) In the liquid detergent of the above (1) or (2), in the component (C), one of R ¹ to R ³ is an alkyl group.

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

(5) In the liquid detergent according to any one of (1) to (4) above, 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 detergent of the above (6), the component (C) is 3-methoxy-3-methylbutanol.

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

(9) In the liquid detergent according to any one of (1) to (8), the component (B) is a linear alkyl benzene sulfonic acid or a salt thereof, an alkanesulfonic acid salt, a polyoxyethylene alkyl ether sulfate ester salt, and α- It is at least one type selected from olefin sulfonates.

(10) In the liquid detergent in any one of the above (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 : a hydrocarbon group having 8 to 18 carbon atoms, X: O, COO or CONH, R ¹² : a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, []: a repeating structure, EO: oxy Ethylene group, PO: oxypropylene group, s: average repetition number of EO, t: average repetition number of PO, s=3-20, t=0-6)

(11) In the liquid detergent of any one of the above (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 : a hydrocarbon group having 8 to 18 carbon atoms, []: repeating structure, EO: oxyethylene group, PO: oxypropylene group, p: average repeat number of EO, q: average repeat number of PO, r: EO Average number of repetitions, p>1, r>1, 0<q≤3, p+r=10-20)

According to the liquid detergent of the present invention, film formation and gelation can be favorably prevented, and the odor is good.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is shown and this invention is demonstrated concretely.

(Liquid cleaner)

The liquid detergent according to the present embodiment comprises (A) component: a nonionic surfactant, (B) component: at least one anionic surfactant selected from sulfonate or sulfuric ester salt, and (C) component: a specific organic solvent. Contains.

The viscosity of the liquid detergent of the present embodiment is not particularly limited, but is preferably 30 to 300 mPa·s, for example. If the viscosity is equal to or less than the above upper limit, the permeability to the fiber product or the like which is the object to be washed increases during coating and washing.

The above-described viscosity value is a value measured at 25°C. Even if it is a viscosity outside the range specified in the present specification, if it is a viscosity within the range specified in the present specification when corrected to the viscosity at 25°C, it shall be included in the scope of the present invention.

The viscosity of the liquid detergent can be measured using a tubular viscometer, a rotary viscometer, etc., particularly preferably a rotary viscometer, and more preferably a rotary viscometer. In this embodiment, as an example, a value measured by a B-type viscometer (manufactured by TOKIMEC INC.) (measurement condition: 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 to 9. When the pH of the liquid detergent is in the range of 4 to 9, the coating cleaning power will be higher. The pH of the liquid detergent is more preferably 6 to 9, and there is an advantage that the liquid appearance stability is improved in this range.

The above-described pH value is a value measured at 25°C. Even if the pH is outside the range specified in the present specification, if it is a pH within the range specified in the present specification when corrected to the pH at 25°C, it shall be included in the scope of the present invention.

The pH of the liquid detergent can be measured by appropriately using a test paper, a test solution, or an electric pH measuring device (such as a pH meter) or other measuring means. In this embodiment, as an example, a value measured by a pH meter (HM-30G, manufactured by DKK-TOA CORPORATION) or the like can be used.

<(A) component: Nonionic surfactant>

(A) component is a nonionic surfactant. The component (A) is used to impart cleaning power to a liquid detergent.

Nonionic surfactants (sometimes referred to as nonionic surfactants, nonionic surfactants, nonionic surfactants, nonionic surfactants, nonionic surfactants, etc.) are surfactants that do not exhibit ionic properties even when dissolved in water. Points to. Examples of nonionic surfactants used in the component (A) include alkylene oxide adducts such as fatty acid alkyl esters, higher alcohols, alkylphenols, higher fatty acids, higher fatty acid alkyl esters or higher amines, and polyoxyethylene polyoxypropylene. Block copolymer, fatty acid alkanol amine, 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-alkyl polyhydroxy fatty acid amide, or alkyl glucoside.

Among them, (A) component is a polyoxyalkylene-type nonionic surfactant represented by the general formula (a1) described later (hereinafter, it may be referred to as (a1) component) or a general formula (a2) described later. A polyoxyalkylene-type nonionic surfactant (hereinafter, it may be referred to as a component (a2)) is preferred. These (A) components may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (A) in the liquid detergent of the present embodiment is 30 mass% or more, preferably 30 to 70 mass%, based on the total mass of the liquid detergent. If the content of the component (A) is 30 mass% or more of the lower limit with respect to the total mass of the liquid detergent, sufficient cleaning power can be exhibited. That is, in the present embodiment, by containing the component (B) and the component (C) described later, film formation or gelation is difficult to occur even when the concentration of the component (A) is increased, so that the component (A) in the liquid detergent is 30% by mass. As described above, it can be set as a liquid detergent having a high cleaning power per liquid amount. Further, when the component (A) in the liquid detergent is set to 70% by mass or less, film formation and gelation can be made more difficult to occur.

Further, it is more preferable that the content of the component (A) is 30 to 60% by mass with respect to the total mass of the liquid detergent, and there is an advantage that sufficient cleaning power can be exhibited within this range. It is particularly preferable that the content of the component (A) is 40 to 50% by mass relative to the total mass of the liquid detergent, and there is an advantage that film formation or gelation can be prevented within this range.

<(a1) component>

In this embodiment, as the component (a1), a compound represented by the following formula can be used.

R ¹¹ -X-[(EO) _s /(PO) _t ]-R ¹² ···(a1)

(Wherein (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 alke having 2 to 6 carbon atoms. [] represents a repeating structure, and [(EO) _s /(PO) _t ] represents that the structure of the compound of the component (a1) has a structure in which EO or PO is repeated in []. EO represents an oxyethylene group and PO represents an oxypropylene group Each compound may have either EO or PO in a repeating structure, or may have both in a mixture When each compound has EO and PO mixedly EO and PO may be arranged in any order, s represents the average number of repetitions of EO, and is selected from a number of 3 to 20. t represents the average number of repetitions of PO, and is selected from the number of 0 to 6 Here, the average number of repetitions refers to the average number of repetitions as the average number of repetitions per molecule, for convenience, since there is a variation in the number (repetition number) containing EO or PO per molecule when preparing the above compound. The average repetition number may be regarded as the molar ratio of EO or PO added to 1 mole of the component (a2) described above at the time of synthesis as the value of the average repetition number, but in order to strictly obtain the average repetition number, a certain number of moles The molecular weight distribution may be determined by gas chromatography or the like for a sample of, and the average of the number of repetitions estimated from the molecular weight may be obtained.)

In formula (a1), the number of carbon atoms of R ¹¹ is preferably 10 to 18 from the viewpoint of improving cleaning power.

R ¹¹ is preferably an alkyl group or an alkenyl group, and may be linear or branched.

As R ¹¹ , raw materials such as primary or secondary higher alcohols, higher fatty acids or higher fatty acid amides are used, and an alkyl group or alkenyl group derived therefrom may be mentioned. Here, a higher alcohol, higher fatty acid, or higher fatty acid amide refers to a higher alcohol, higher fatty acid or higher fatty acid amide having a carbon chain having 5 or more carbon atoms as a standard.

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 in the compound represented by (a1), the cleaning power of the liquid detergent increases. 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, the number of carbon atoms of R ¹¹ is preferably 9 to 18. By using these in the compound represented by (a1), the cleaning power of the liquid detergent increases. Further, the number of carbon atoms of R ¹¹ is more preferably 11 to 18, and there is an advantage that the appearance stability is improved 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 of 3 to 20. When s exceeds 20, the HLB value of the liquid detergent (affinity between the aqueous layer and the hydrophobic layer of the surfactant) becomes too high, and the cleaning power tends to decrease. When s is less than 3, the raw material odor of the component (A) itself tends to be liable to deteriorate. Moreover, it is preferable that s is 5-18.

t is a number from 0 to 6. When t exceeds 6, the storage stability of the liquid detergent under high temperature tends to decrease. In addition, t is preferably the number of 0-3.

EO and PO may be mixed and arranged, and (EO) _s / (PO) _t may be arranged in a so-called random phase in which EO and PO do not have regularity in the arrangement. Further, EO and PO may each form a block in which a predetermined number is arranged, and the blocks may be arranged in a so-called block shape.

In the component (a1), the distribution of the number of moles added of EO or PO is not particularly limited, and it is liable to fluctuate depending on the reaction method in producing the component (a1). Here, the number of moles added refers to the number of moles of an additional group (a group added to the compound, here EO or PO) per 1 mole of the raw material. The average number of added moles is the average of the number of added moles for each molecule of the compound, and when an additional group is added at the time of preparation of the compound, the value of the ratio of the number of moles of the addition group to 1 mole of the compound may be regarded as the average number of added moles. When a precise value is required for the average number of added moles, the molecular weight for each molecule contained in the compound of a certain number of moles is measured by chromatography, the number of added moles for each molecule is estimated from the molecular weight, and the value is averaged. The distribution of the number of added moles is a distribution of the number of added moles for each molecule contained in a certain amount of the compound, but in the present embodiment, the narrow ratio is used as an index below. The molecular weight of each molecule contained in the compound of a certain number of moles is measured by chromatography or the like, and the number of added moles is estimated. The number of moles added of the addition group of the molecule, which exists most on a mass basis among all compounds, is called "nlmax". The sum of the masses (nlmax-1 to 1) of the molecules of (nlmax-1), nlmax, and (nlmax+1), respectively, is obtained. The ratio of "nlmax-1 to 1" with respect to the mass of all molecules in the compound is called the narrow ratio.

The distribution of the added mole number of EO or PO is, for example, using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, using ethylene oxide or propylene oxide as a raw material (primary or secondary higher alcohol, higher fatty acid, higher fatty acid). Amide, etc.) tends to have a relatively wide distribution.

The distribution of the added mole number of EO or PO is, for example, Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , Tl ^{3 +} , Co ^{3 +} , Sc ^{3 +} , La ^{3 +} described in Japanese Patent Publication No. Hei 6-15038. When ethylene oxide or propylene oxide is added to the raw material using a specific alkoxylation catalyst such as magnesium oxide to which a metal ion such as Mn ^{2 +} is added, there is a tendency for a relatively narrow distribution.

When the liquid detergent has a narrower (narrower) distribution of the number of moles added, that is, a large narrower ratio, the chemical properties of the liquid detergent are stable, and the cleaning power for a specific compound becomes stronger. On the other hand, the wider distribution of the number of moles added (broadcast), that is, the smaller the narrow ratio, the more liquid detergent contains compounds of various chemical properties, so that various contaminations can be cleaned. Therefore, it is preferable to design the distribution of the number of moles added according to the purpose of the liquid detergent.

The specific example of the component (a1) is further shown. Mitsubishi Chemical Corporation's Diadol (brand name, C13 (C represents the number of carbon atoms, the same hereinafter)), Shell product Neodol (brand name, a mixture of C12 and C13) or Sasol Limited's Safol 23 (brand name, C12 and C13) Addition of ethylene oxide equivalent to 12 mol or 15 mol with respect to 1 mol of alcohol such as a mixture); Procter & Gamble Co. Addition of ethylene oxide equivalent to 12 mol or 15 mol to 1 mol of natural alcohol such as CO-1214 or CO-1270 (brand name) of the product; What added 7 moles of ethylene oxide to 1 mole of C13 alcohol obtained by subjecting the C12 alkene obtained by trimerizing butene to the oxo method (trade name: Lutensol TO7, manufactured by BASF SE); What added 9 mol of ethylene oxide to 1 mol of C10 alcohol obtained by subjecting pentanol to a Guerbet reaction (trade name: Lutensol XP90, manufactured by BASF SE); What added 7 mol of ethylene oxide to 1 mol of C10 alcohol obtained by providing pentanol to the Guerbet reaction (trade name: Lutensol XL70, manufactured by BASF SE); What added 6 moles of ethylene oxide to 1 mole of C10 alcohol obtained by providing pentanol to the Guerbet reaction (trade name: Lutensol XA60, manufactured by BASF SE); Addition of ethylene oxide equivalent to 9 moles or 15 moles per mole of secondary alcohol having 12 to 14 carbon atoms (trade names: SOFTANOL 90, SOFTANOL 150, manufactured by NIPPON SHOKUBAI CO., LTD.); What added 15 moles of ethylene oxide to 1 mole of palm fatty acid methyl (lauric acid/myristic acid = 8/2) using an alkoxylation catalyst (polyoxyethylene palm fatty acid methyl ester (EO 15 moles)) ), etc.

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

<(a2) component>

In this embodiment, as the component (a2), a compound represented by the following formula can be used.

R ¹³ -O-[(EO) _p /(PO) _q ]-(EO) _r -H ···(a2)

(In 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 structure of the compound of the component (a1) [] It indicates that it has a structure in which EO or PO is repeated in. Here, EO represents an oxyethylene group and PO represents an oxypropylene group Each compound may have only one of EO and PO in the repeating structure, and both are mixed. When each compound has EO and PO mixed, EO and PO may be arranged in any order, p denotes the average number of repetitions of EO in the repeating structure, and q is the average of PO in the repeating structure. Represents the number of repetitions, r represents the average repetition number of EO other than the repetition structure, p, q, and r are numbers satisfying p>1, r>1, 0<q≤3, p+r=10-20 .

In the formula (a2), 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 and PO is preferably 0.1 to 0.5 in a ratio expressed by q/(p+r). When the ratio expressed as q/(p+r) is equal to or greater than 0.1, bubbles are not excessively generated, so that it is easy to optimize the generation of bubbles. By the above 0.5 value or less, it becomes easy to obtain an appropriate viscosity, and gelation can be suppressed more favorably. It is more preferable that the ratio of EO and PO is 0.1 to 0.3.

EO and PO may be mixed and arranged, and (EO) _p /(PO) _q may be added in a so-called random phase in which EO and PO do not have regularity in the arrangement. Further, EO and PO may each form a block in which a predetermined number is arranged, and the blocks may be added in a so-called block shape in which the blocks are arranged.

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

By using the component (a2) as the component (A), the liquid detergent tends to have an appropriate viscosity, so that gelation can be better suppressed. In addition, the foaming property is improved and the biodegradability is also improved.

<(B) component: at least one anionic surfactant selected from sulfonate or sulfuric ester salt>

The component (B) contained in the liquid detergent of the present embodiment is one or more anionic surfactants selected from component: sulfonate or sulfuric ester salt. When the liquid detergent contains the component (B), film formation and gelation can be favorably prevented.

Anionic surfactants (anionic surfactants, anionic surfactants, anionic surfactants, anionic surfactants, anionic surfactants, etc.) are surfactants that become anionic when dissolved in water. It has a hydrophilic group.

As the anionic surfactant used in the component (B), for example, straight-chain alkyl benzenesulfonic acid or a salt thereof; α-olefin sulfonate; Linear or branched alkyl sulfate ester salts; Alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; An alkane sulfonate having an alkyl group; Or α-sulfo fatty acid ester salt, etc. are preferable. The ester salt of sulfuric acid or sulfo fatty acid of the above-described compound refers to that the sulfuric acid group or fatty acid group of the compound 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 alkanol amine salts such as monoethanol amine or diethanol amine.

As the linear alkyl benzenesulfonic acid or its salt, the linear alkyl group preferably has 8 to 16 carbon atoms, and particularly preferably 10 to 14 carbon atoms.

The α-olefin sulfonate is preferably one having 10 to 20 carbon atoms. As the alkyl sulfate ester salt, it is preferable that the alkyl group has 10 to 20 carbon atoms.

As the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt used in the component (B), it may have a straight or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms. Moreover, what has an oxyethylene group or an oxypropylene group may be sufficient.

As the alkanesulfonic acid salt, the alkyl group preferably has 10 to 20 carbon atoms, and more preferably 14 to 17 carbon atoms. Among them, those in which the alkyl group is a secondary alkyl group (ie, secondary alkanesulfonic acid salt) are particularly preferred.

As the α-sulfo fatty acid ester salt, the fatty acid residue preferably has 10 to 20 carbon atoms.

It is particularly preferable to use at least one compound selected from linear alkyl benzene sulfonic acid or a salt thereof, alkanesulfonic acid salt, polyoxyethylene alkyl ether sulfate ester salt, and α-olefin sulfonic acid salt among these for the component (B). In particular, when linear alkylbenzenesulfonic acid or a salt thereof is used for component (B), stability is high and odor is suppressed, but the effect of increasing stability is high. By using a polyoxyethylene alkyl ether sulfate ester salt for the component (B), the stability is high and the odor is suppressed, but the effect of suppressing the odor is particularly high.

As (B) component, you may use other non-soap-type anionic surfactants other than the above. Examples of non-soap anionic surfactants other than the above include carboxylic acid types such as alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkyl (or alkenyl) amide ether carboxylate, and acylaminocarboxylate. Anionic surfactants; And phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkylphenyl phosphoric acid ester salts, or glycerin fatty acid ester monophosphoric acid ester salts.

These (B) components can be easily obtained in the market.

These (B) components may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (B) in the liquid detergent of the present embodiment is preferably 1 to 20 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 the formation of a film or gelation of the liquid detergent, and the low-temperature stability of the liquid detergent increases. The content of the component (B) is more preferably 2 to 10% by mass, and within this range, it is possible to achieve both the formation of a film, prevention of gelation, and low-temperature stability at a high level. It is more preferable that the content of the component (B) is 3 to 8% by mass.

In the liquid detergent of the present embodiment, the mass ratio (hereinafter sometimes referred to as A/B ratio) represented by the component (A)/component (B) is preferably 3 to 50. If the A/B ratio is 3 or more, it can be prevented favorably by film formation or gelation, and if it is 50 or less, the odor of the object to be washed is more difficult to damage. It is more preferable that the A/B ratio is 5-20. Moreover, it is more preferable that the A/B ratio is 7-15.

<(C) component: specific organic solvent>

The component (C) contained in the liquid detergent of this embodiment is an organic solvent represented by the following general formula (I). When the liquid detergent of the present embodiment contains the component (C), film formation and gelation can be favorably prevented, and odor can be improved.

In more detail, the (C) component has low volatility. For this reason, since the liquid detergent contains the component (C), even when left in an open system, film formation and gelation are unlikely to occur. In addition, by including the component (C) in the liquid detergent, it is difficult to impair the fragrance of the flavoring agent incorporated in the liquid detergent. In addition, since the liquid detergent contains the component (C), it is difficult for the odor of the component (C) to remain in the object to be washed.

(In 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) wherein, R ¹ ~R ³ are either both hydrogen or one is the alkyl group and the other two are each, i.e. R ¹ ~R ³ of two or three (or more, at least two hydrogen atoms It is preferable that) is a hydrogen atom. If two or ^three of R ¹ to R 3 are hydrogen atoms, film formation or gelation can be better prevented even if left in an open system.

When any one of R ¹ to R ³ is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 2, more preferably 1. When the number of carbon atoms of R ¹ to R ³ is within the above range, even when left in an open system, film formation and gelation can be better prevented.

R ⁴ is preferably a hydrogen atom from the viewpoint of better preventing film formation or gelation even when left in an open system.

(C) As a component, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol , 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol or 3-methoxy-1-propylbutanol R ⁴ in formula (I) such as a hydrogen atom; 3-methoxybutylacetate, 3-methoxy-3-methylbutylacetate, 3-methoxy-3-ethylbutylacetate, 3-methoxy-3-propylbutylacetate, 3-methoxy-2-methylbutylacetate , 3-methoxy-2-ethylbutylacetate, 3-methoxy-2-propylbutylacetate, 3-methoxy-1-methylbutylacetate, 3-methoxy-1-ethylbutylacetate, 3-methoxy- The thing in which R ⁴ in Formula (I), such as 1-propylbutyl acetate, is an acetyl group, etc. are mentioned.

Among them, as the component (C), 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, or 3-methoxy-3 -Methylbutyl acetate is preferred. Moreover, as (C) component, 3-methoxy-3-methylbutanol is more preferable.

These (C) components may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the component (C) in the liquid detergent of the present embodiment is preferably 1 to 20 mass% with respect to the total mass of the liquid detergent. When the content of the component (C) is 1% by mass or more, it is easier to prevent film formation and gelation of the liquid detergent, and the low-temperature stability of the liquid detergent increases. When the content of the component (C) is 20% by mass or less, the odor of the component (C) is more difficult to migrate to the object to be washed, and the odor of the liquid detergent itself is more difficult to damage. It is more preferable that content of (C) component is 2-15 mass %. It is more preferable that the content of the component (C) is 3 to 10% by mass.

In addition, the component (C) is preferably used in combination with a water-miscible organic solvent (C') other than the component (C), and among them, it is more preferably used in combination with ethanol. When (C)+(C')<5, (C)/(C') is preferably 4 or more. Further, when 5≦(C)+(C′), (C)/(C′) is preferably 0.5 to 10, and more preferably 1 to 4. By being within the above range, the prevention of odor and film formation is further improved.

In the liquid detergent of the present embodiment, the mass ratio (hereinafter sometimes referred to as C/A ratio) represented by component (C)/component (A) is 0.04 to 0.5. When the C/A ratio is less than 0.04, film formation or gelation of the liquid detergent cannot be prevented satisfactorily, and when the value exceeds 0.5, the odor of the liquid detergent is liable to be damaged. It is preferable that the C/A ratio is 0.04 to 0.3. It is more preferable that the C/A ratio is 0.04 to 0.18.

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

<arbitrary ingredients>

The liquid detergent of this embodiment can contain arbitrary components other than (A)-(C) components as needed. As optional components, surfactants (optional surfactants) other than components (A) to (B), viscosity reducing agents, solubilizing agents, sequestering agents, antioxidants, tactile improvers, optical brighteners, recontamination inhibitors, enzymes, Flavoring agents, coloring agents, emulsifying agents, extracts, pH adjusting agents, pearling agents, or soil release agents.

As an arbitrary surfactant, a cationic surfactant, an amphoteric surfactant, a higher fatty acid salt, etc. are mentioned.

Cationic surfactants (cation surfactants, cationic surfactants, cationic surfactants, cationic surfactants, cationic surfactants, etc.) are surfactants that become cationic when dissolved in water, and cationic It has a hydrophilic group. As the cationic surfactant, cationic surfactants, such as an alkyl trimethyl ammonium salt, a dialkyl dimethyl ammonium salt, an alkyl benzyl dimethyl ammonium salt, or an alkylpyridinium salt, are mentioned, for example. 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 is one that 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 a hydrophilic group of both an anion and a cation. Examples of amphoteric surfactants include alkyl betaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type or phosphoric acid type amphoteric surfactant, etc. Can be mentioned. In the liquid detergent, the content of the amphoteric surfactant is preferably 0.05 to 5.0 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. When the content of the higher fatty acid salt is 0.01% by mass or more, the defoaming property at the time of washing increases, and when the content exceeds 5% by mass, the formation of a film or gelation of the liquid detergent tends to occur.

Examples of the reducing agent or solubilizing agent include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, toluenesulfonic acid salt, xylenesulfonic acid salt, cumene sulfonic acid salt, or substituted or unsubstituted naphthalenesulfonic acid salt. . Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, or alkanol amine salt.

The viscosity reducing agent or solubilizing agent may be used singly or in combination of two or more.

The content of the viscosity reducing agent or the solubilizing agent in the liquid detergent of the present embodiment is preferably 0.01 to 15% by mass based on the total mass of the liquid detergent. Within the above range, it is possible to further prevent the formation of a film of the liquid detergent.

As an alkali agent, an alkanol amine is mentioned, for example. Examples of the alkanol amine include monoethanol amine, diethanol amine, or triethanol amine. Alkali agents may be used alone or in combination of two or more.

The content of the alkali agent in the liquid detergent of the present embodiment is preferably 0.5 to 5% by mass, for example, based on the total mass of the liquid detergent.

As a metal ion scavenger, malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, etc. are mentioned, for example.

The metal ion scavenger may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the metal ion scavenger in the liquid detergent of the present embodiment is preferably 0.1 to 20 mass% with respect to the total mass of the liquid detergent.

The antioxidant is not particularly limited, but a phenolic antioxidant is preferred from the viewpoint of good cleaning power 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 dibutylhydroxy Toluene and dl-α-tocopherol are particularly preferred.

Antioxidants may be used singly or in combination of two or more.

The content of the antioxidant in the liquid detergent of the present embodiment is preferably 0.01 to 2 mass% with respect to the total mass of the liquid detergent.

Examples of the texture improving agent include silicones such as dimethyl silicone, polyether-modified silicone, or amino-modified silicone.

The content of the feel improver in the liquid detergent of the present embodiment is preferably 0 to 5% by mass based on the total mass of the liquid detergent.

Examples of the optical brightener include distyrylbiphenyl type optical brighteners.

Fluorescent whitening agents may be used alone or in combination of two or more.

The content of the optical brightener in the liquid detergent of the present embodiment is preferably 0 to 1% by mass based on the total mass of the liquid detergent.

Examples of the recontamination inhibitor include polyvinylpyrrolidone or carboxymethyl cellulose.

Recontamination inhibitors may be used singly or in combination of two or more.

The content of the recontamination inhibitor in the liquid detergent of the present 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, or these preparations.

The flavoring agent is not particularly limited as long as it is conventionally used in liquid detergents, and for example, a substance selected from compounds such as hydrocarbons, ethers, alcohols, phenols, phenol ethers, aldehydes, acetals, ketals, ketones, lactones, esters or sulfur-containing compounds. Or it is appropriately selected from natural perfumes or synthetic perfumes. As examples of these, perfume compositions A to D and the like described in Tables 11 to 18 of JP 2002-146399 A can be cited.

The content of the flavoring agent in the liquid detergent of the present embodiment is preferably 0.1 to 1 mass% with respect to the total mass of the liquid detergent.

As a colorant, 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 are brand names), are mentioned.

The content of the colorant in the liquid detergent of the present embodiment is preferably 0.00005 to 0.005% by mass with respect to the total mass of the liquid detergent.

Examples of the emulsifier include polystyrene emulsion or polyvinyl acetate emulsion, and an emulsion having a solid content of 30 to 50% by mass is suitably used. Examples of the emulsifier of the emulsion include a polystyrene emulsion (trade name: Saivinol RPX-196 PE-3, solid content 40% by mass, manufactured by Saiden Chemical Co., Ltd.).

The content of the emulsifier in the liquid detergent of this embodiment is preferably 0.01 to 0.5% by mass based on the total mass of the liquid detergent.

As extracts, the extracts include Daum tree, bilberry leaf, echinacea, gold, yellow wall tree, yellow lotus, allspice, organo, peach tree, chamomile, honeysuckle, gosam, hyeonggae, overgrown, laurel tree, black oak, burdock, campri, casualty seed. , Cucumber grass, peony, ginger, yangmi, elderberry, sage, mistletoe, creation, thyme, jimo, clove, whole mandarin orange, tea tree, barberry, 300 vinegar, namcheonchok, frankincense, copper stalk, white feather hydra, windbreak greens, Dutch amaranth , Hops, rosewood, mountain grapes, magnetized wood, lemon balm, pan fan, wild sesame, eucalyptus, lavender, rose, rosemary, leaf egg, cedar, balsam fir, white line, dassari, single axis, jingyo, And plant extracts such as taiwanese-style tree, stalk, mountain dry, beggar vine, licorice or St. John's wort.

The content of the extracts in the liquid detergent of the present embodiment is preferably 0 to 0.5% by mass with respect to the total mass of the liquid detergent.

In order to make the pH of the liquid detergent of the present embodiment a desired value, a pH adjuster may be blended. However, when the liquid detergent reaches a desired pH with only the above-described components, it is not necessary to use a pH adjuster.

Examples of the pH adjuster include acidic compounds such as sulfuric acid and hydrochloric acid; Alkanol amines such as monoethanol amine, diethanol amine, and triethanol amine, and alkaline compounds such as sodium hydroxide or potassium hydroxide are mentioned. From the viewpoint of enhancing the stability over time of the liquid detergent, sulfuric acid, sodium hydroxide, potassium hydroxide or alkanol amine is preferable, and sulfuric acid or sodium hydroxide is more preferable.

These pH adjusters may be used individually by 1 type, and may be used in combination of 2 or more types. The content of the pH adjusting agent in the liquid detergent is appropriately selected depending on the desired pH.

As a modified form of the liquid detergent of this embodiment, a liquid detergent containing at least components (A) to (C) and not containing water may be used. In this case, the liquid detergent may be dispersed in water immediately before use, or may be dissolved in water for washing when used.

(Method of manufacturing liquid detergent)

As a method for producing the liquid detergent of the present embodiment, a method of dispersing components (A) to (C) and optional components in a dispersion medium such as water is exemplified. As a manufacturing method of a liquid detergent, the following method is mentioned, for example. The above-described components (B) to (C) are dispersed in a small amount of water. At this time, if necessary, any of the above-described components is also dispersed in this water. After visually confirming that these components are sufficiently dispersed in water, this dispersed aqueous solution is adjusted to an arbitrary pH. To adjust the pH, the above-described pH adjuster may be added, or another acid, alkali, or pH buffering agent may be added. Following the aqueous solution whose pH was adjusted, the component (A) is dispersed. After that, it is further adjusted to an arbitrary pH serving as the final pH of the liquid detergent, and water is further added to obtain a liquid detergent. It is preferable to add water so that it may become 10 to 70 mass% with respect to the total mass of the liquid detergent, and it is more preferable to add it so that it may become 20 to 40 mass %.

(How to use liquid detergent)

The method of using the liquid detergent of the present embodiment (cleaning method using the liquid detergent of the present embodiment) is the same as the method of using a general liquid detergent.

For example, a method of putting a liquid detergent together with the object to be washed in water and washing it with a washing machine, a method of applying the liquid detergent directly to the object to be washed, a method of dissolving the liquid detergent in water to make a washing solution, and immersing the object to be washed in the washing solution. Method, etc. are mentioned. Further, a liquid detergent may be applied to the object to be washed, allowed to stand appropriately, and then washed using a washing machine or the like. In the case of washing with a washing machine by putting a liquid detergent together with the object to be cleaned, the amount of the liquid detergent to water varies depending on the components of the liquid detergent, but as a standard, the liquid detergent is 0.03 to 1% by volume based on the volume of water. The cleaning effect is obtained. The appropriate value varies depending on the amount or material of the object to be cleaned, the severity of the contamination, the component of the liquid detergent, or the concentration of the liquid detergent, but as a standard, it is used for cleaning. In the case of washing the amount enough to be immersed in water, it is preferable to perform washing for 5 to 30 minutes about 1 to 4 times. In the method of immersing the object to be washed by dissolving the liquid detergent in water as a cleaning solution, the content of the liquid detergent may be the same as that of the washing machine described above, but the more concentrated liquid detergent (more content) is more effective. The liquid detergent is preferably 0.06 to 5% by volume based on the volume of water.

Although it does not specifically limit as an object to be washed, For example, the liquid detergent of this embodiment can be suitably applied to textile products, such as medical care, woven fabrics, sheets, curtains, or carpets.

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, high cleaning power 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 favorably prevented.

Further, since the liquid detergent contains the component (C), the odor is good.

Example

Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Used raw materials)

<(A) component: Nonionic surfactant>

A-1: 12 moles of ethylene oxide added to 1 mole of natural alcohol (LMAO). What was synthesized in Synthesis Example 1 below.

Synthesis Example 1 Synthesis of A-1

Procter & Gamble Co. 861.2 g of CO-1214 (brand name) of the product and 2.0 g of a 30% by mass NaOH aqueous solution based on the total mass of the liquid detergent were put into a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating the inside of this container for 30 minutes at a temperature of 100°C and a pressure of 2.0 kPa or less, the temperature was raised to 160°C. Next, while stirring the reaction liquid in the container, 760.6 g of ethylene oxide (gas phase) was gradually added to the reaction liquid. At this time, ethylene oxide was added to the blowing tube while controlling 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 vessel 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 this container to 100°C or less, 70% by mass p-toluenesulfonic acid was added and neutralized so that the pH of the 1% by mass aqueous solution of the reactant was about 7 to obtain A-1 (LMAO).

A-2: To 1 mol of palm fatty acid methyl (a mixture of methyl laurate/methyl myristic = 8/2 by mass ratio), 15 mol of ethylene oxide was added using an alkoxylation catalyst (methyl ester Ethoxylate, MEE). What synthesized in Synthesis Example 2 below.

Synthesis Example 2 Synthesis of A-2

It synthesized according to the synthesis method (corresponding to sample D) described in Japanese Patent Application Laid-Open No. 2000-144179.

Composition is _{2.5MgO · Al 2 O 3 · wH} 2 O , magnesium hydroxide, alumina (KYOWADO 300 (trade name), Kyowa Chemical Industry Co., Ltd. product) was calcined under an hour, a nitrogen atmosphere at 600 ℃ calcined alumina hydroxide -Obtained a magnesium (unmodified) catalyst. 2.2 g of this calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were put into a 4 L autoclave, and the inside of the autoclave The catalyst was reformed at. Subsequently, after replacing the inside of this autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180° C. and the pressure at 0.3 MPa, followed by reaction while stirring.

The obtained reaction solution was cooled to 80° C., and 159 g of water and 5 g of activated clay and diatomaceous earth were each added as a filter aid, and then the catalyst was collected by filtration to obtain A-2 (MEE).

A-3: SOFTANOL 90 (brand name, product of NIPPON SHOKUBAI CO., LTD.). Ethylene oxide equivalent to 9 moles added to 1 mole of a secondary alcohol having 12 to 14 carbon atoms.

A-4: Lutensol XP90 (trade name, BASF SE product). Ethylene oxide equivalent to 9 moles added to 1 mole of alcohol having 10 carbon atoms obtained by providing pentanol to the Guerbet reaction.

A-5: Block addition of ethylene oxide so that the average number of added moles is 9 moles, propylene oxide so that the average number of moles added is 2 moles, and ethylene oxide is added so that the average number of moles added is 9 moles per 1 mole of primary alcohol having 10 to 14 carbon atoms. What I ordered. R ^{13 in} formula (a2) is a C10-14 linear alkyl group, p=9, q=2, r=9. In the table, it is described as an alcohol EOPO adduct.

<(B) component: Anionic surfactant>

B-1: LAS, straight-chain alkyl (carbon number 10-14) benzenesulfonic acid (brand name: LIPON LH-200 (LAS-H), pure powder 96% by mass, manufactured by Lion Corporation), average molecular weight 322 (when preparing a liquid detergent , It is neutralized by sodium hydroxide, a pH adjuster, to become a sodium salt).

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

Synthesis Example 3 Synthesis of B-2

Neodol 23 (brand name, C12, 13 alcohol (mixture of 1/1 mass ratio of alcohol with 12 carbon atoms and alcohol with 13 carbon atoms), 20% by mass, Shell product) 400g as raw material alcohol in 4L autoclave, and potassium hydroxide 0.8 g of catalyst was added. The inside of this autoclave was purged with nitrogen, and the temperature was raised while stirring. Thereafter, 272 g of ethylene oxide was introduced while maintaining 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 added mole number of ethylene oxide of 2.

280 g of the obtained alcohol ethoxylate was put into a 500 mL flask equipped with a stirring device, and 67 g of liquid anhydrous sulfuric acid (sulfane) after nitrogen substitution was slowly added dropwise while maintaining the reaction temperature at 40°C. After completion of the dropwise addition, the contents of this 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 moles added of ethylene oxide of this B-2 was evaluated by measuring the ethylene oxide narrow ratio. The ethylene oxide narrow rate was determined as follows.

The number of moles of ethylene oxide added in the ethylene oxide adduct which is the most present on a mass basis among all the ethylene oxide adducts constituting AES is referred to as "nlmax". The sum of the masses (nlmax-1 to 1) of ethylene oxide adducts having the added moles of ethylene oxide (nlmax-1), nlmax, and (nlmax+1), respectively, is calculated. The ratio of "nlmax-1 to 1" to the mass of all the ethylene oxide adducts in AES is referred to as the narrow ratio.

The ethylene oxide narrow ratio of B-2 obtained here was 35 mass %.

B-3: Grade 2 alkanesulfonic acid Na (SAS), SAS30 (trade name, manufactured by Clariant (Japan) K.K.).

B-4: Polyoxyalkylene alkyl ether sulfuric acid ester monoethanol amine salt (linear alkyl having 10 to 14 carbon atoms, PO average added mole number 1, EO average added 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 (C) component>

C'-1: Ethanol (trade name: 95-degree synthesis of specific alcohol, manufactured by Japan Alcohol Trading Co., Ltd.).

C'-2: Butylcarbitol (manufactured by Nippon Nyukazai Co., Ltd.).

<pH adjuster>

Sodium Hydroxide or Sulfuric Acid: Appropriate amount (the amount required to adjust to the pH in the table). The total of the pH adjusters in the liquid detergents of each example was 0 to 3% by mass.

<water>

Purified water: Balance (amount to make the total amount of the 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 (brand name), Kyowa Hakko Kogyo Co., Ltd. Product ...1% by mass.

Monoethanol amine: NIPPON SHOKUBAI CO., LTD. Product ...1% by mass.

Palm fatty acid: NOF CORPORATION product...1% by mass.

Palmitic acid: NOF CORPORATION product ...0.1% by mass.

Flavoring agent: Perfume composition A...0.4% by mass described in Tables 11 to 18 of JP 2002-146399 A.

Dibutylhydroxytoluene (BHT): SUMILZER BHT-R (brand name), Sumitomo Chemical Co., Ltd. Product ···0.05% by mass.

Lactic acid: JUNSEI CHEMICAL CO., LTD. Product ...1% by mass.

Colorant: Green No. 3, Kishi Kasei Co., Ltd. Product ...0.0002% by mass.

Enzyme: Coronase (brand name), Novozymes A/S product: 0.6% by mass.

Citric acid: Liquid citric acid (trade name), Ipposha Oil Industries Co., Ltd. Product ...0.1% by mass.

(Assessment Methods)

<Stability>

10 g of the liquid detergent of each example was placed in a plastic container (5 cm long x 5 cm wide x 3 cm high), and stored for 40 hours in a constant temperature and humidity room at 25°C and 30% RH. The plastic container used in the test has an open top. After each of these liquid detergents was stored in a constant temperature and humidity room for 40 hours, stability was evaluated according to the following evaluation criteria.

≪Evaluation criteria≫

(Double-circle): Film formation and gelation do not occur, it is uniformly transparent, and has fluidity.

(Circle): Although turbidity is seen, film formation and gelation do not occur, and there is fluidity.

?: Gelation does not occur, there is fluidity, but a film is formed on the surface.

×: Gelation occurs, and fluidity is remarkably reduced.

<Odor>

Ten commercially available cotton towels (100% cotton) were placed in a two-tank washing machine (trade name: CW-C30A 1, manufactured by Mitsubishi Electric Corporation), and 12 L of tap water and 8 mL of a liquid detergent of each example were placed in the two-tank washing machine. The cotton towel was washed in this washing machine with a weak flow of water for 10 minutes for washing time, for 1 minute for spin-drying, for storage rinsing (once, for 3 minutes each), and for 1 minute for spin-drying. The temperature of the tap water used was 25°C. This washing operation was repeated 5 times. After performing the washing operation 5 times (after dehydration), a cotton towel was used as a test cloth.

Separately, changing to the liquid detergent of each example, using 16 mL of a 20% by mass aqueous solution of a nonionic surfactant (an alcohol ethoxylate obtained by adding 15 moles of ethylene oxide with an average number of moles added to 1 mole of lauryl alcohol). A cotton towel subjected to operation 5 times was used as a control cloth.

Ten panelists sensory evaluated the test cloth and the control cloth according to the following evaluation criteria. The average score of the evaluation points of 10 panelists was calculated|required, and 3.5 points or more were set as ◎, 3.0 points or more and less than 3.5 points were set as △, 2.5 points or more and less than 3.0 points were set as △, and less than 2.5 points were set as x.

≪Evaluation criteria≫

1 point: The evaluation fabric feels a very strong off-flavor (an odor different from the flavoring agent) than the control fabric.

2 points|pieces: The evaluation cloth feels off-flavor than the control cloth.

3 points|pieces: The evaluation fabric felt slightly off-flavor than the control fabric.

4 points: The off-flavor of the evaluation fabric and the off-flavor of the control fabric were equivalent.

5 points|pieces: The one of the control fabric feels an off-flavor 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, (B) component, (C) component (or (C') component, and part of water were put in a 500 mL beaker, and this was stirred with a magnetic stirrer (made by MITAMURA KOGYO INC.). , PTS, monoethanolamine, and palm fatty acid were added to this beaker, and then a pH adjuster was added to adjust the pH to 7. The remainder of common components other than enzymes was added to this beaker, and the total amount was 95% by mass while stirring. Water was added, and a pH adjuster was added to adjust the pH in Tables 1 to 2. Next, an enzyme was added to this beaker, and the balance of water was added so that the total amount was 100% by mass to obtain a liquid detergent of each example.

The obtained liquid detergent was evaluated for stability and odor, and the results are shown in the table.

In addition, the composition in the table is the net content conversion amount of each component.

(Examples 22 to 23)

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

In Tables 1 to 2, about the evaluation result of odor, the average score was described at the upper end and the evaluation was described at the lower end.

As shown in Tables 1 to 2, in Examples 1 to 21 to which the present invention was applied, the evaluation of stability was "○" or "◎", and film formation and gelation were satisfactorily suppressed. Moreover, in Examples 1 to 21, the evaluation of odor was "○" or "◎", and the off-flavor derived from the component (C) was suppressed.

On the other hand, in Comparative Example 1 not containing the component (B), the evaluation of the stability was "Δ", and in Comparative Example 2 using ethanol, the evaluation of the stability was "X" by changing to the component (C). In addition, in Comparative Example 3 in which butylcarbitol was used as a component (C), the odor evaluation was "x". In Comparative Example 4 in which C/A was 0.02, the evaluation of stability was "Δ", and in Comparative Example 5 in which the 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.

(Industrial availability)

According to the liquid detergent of the present invention, film formation and gelation can be satisfactorily prevented, and since it has a good odor, it can be widely used in a field where a detergent is used in households and industries.

Claims (11)

(A) component: 30 mass% or more of nonionic surfactant, (B) component: at least one anionic surfactant selected from sulfonate and sulfate ester salt, and (C) component: represented by the following general formula (I) A liquid detergent comprising an organic solvent to be used, and a mass ratio of the component (C) to the component (A) of 0.04 to 0.5.

[In 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] The method of claim 1,
The component (C) is a liquid cleaning agent, characterized in that the R ¹ ~R of two or three of the hydrogen atoms in ^three. The method according to claim 1 or 2,
In the component (C), one of R ¹ to R ³ is an alkyl group. The method of claim 3,
The (C) component is a liquid detergent, characterized in that the alkyl group has 1 or 2 carbon atoms. The method according to claim 1 or 2,
The (C) component is a liquid detergent, characterized in that the R ⁴ is a hydrogen atom. The method according to claim 1 or 2,
The liquid detergent, characterized in that the component (C) is 3-methoxybutanol or a derivative thereof. The method of claim 6,
The liquid detergent characterized in that the component (C) is 3-methoxy-3-methylbutanol. The method according to claim 1 or 2,
A liquid detergent, wherein the content of the component (C) in the liquid detergent is 1 to 20% by mass relative to the total mass of the liquid detergent. The method according to claim 1 or 2,
The liquid detergent, characterized in that the component (B) is selected from at least one selected from linear alkyl benzenesulfonic acid or its salt, alkanesulfonic acid salt, polyoxyethylene alkyl ether sulfate ester salt, and α-olefin sulfonate. The method according to claim 1 or 2,
The liquid detergent, characterized in that 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: oxy Ethylene group, PO: oxypropylene group, s: average repetition number of EO, t: average repetition number of PO. s=3-20, t=0-6] The method according to claim 1 or 2,
The liquid detergent, characterized in that 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 : a hydrocarbon group having 8 to 18 carbon atoms, []: a repeating structure, EO: an oxyethylene group, PO: an oxypropylene group, p: an average repetition number of EO, q: an average repetition number of PO, r: of EO Average number of reps. p>1, r>1, 0<q≤3, p+r=10-20]