JP2010185063A - Liquid cleanser composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition having good detergency and low temperature storage stability.
SOLUTION: (a) a compound represented by the compound of the general formula (1), (b) a linear hydrocarbon group having 8 to 18 carbon atoms capable of forming an ionically complex with the component (a) A surfactant having a straight chain hydrocarbon group having 8 to 18 carbon atoms other than the components (c), (a), and (b), (d) a phase stabilizer, and a liquid detergent containing water Composition.
R ^a1 O- (PO) _m1- (EO) _n1 SO ₃ M (1) [R ^a1 is a straight hydrocarbon group having 8 to 18 carbon atoms, and the oxygen atom of R ^a1 O- is the first carbon of R ^a1 Bonded to an atom, PO and EO are oxypropylene and oxyethylene groups, m1 is the average number of moles of PO added, 0.1 to 1, n is the average number of moles of EO added to 0.5 to 3, and M is positive ion〕
[Selection figure] None

Description

  The present invention relates to a liquid detergent composition.

  In recent years, from the viewpoint of reducing environmental impact, concentrated liquid cleaning agents in which the concentration of a surfactant is increased and the amount of resin in a container is reduced are preferred and used. In addition, body cleaners and dishwashing liquid cleaners use an anionic surfactant polyoxyalkylene alkyl ether sulfate type surfactant as the main component from the viewpoints of detergency and hand roughening. In particular, liquid detergents for washing dishes are anionic surfactants such as amine oxide surfactants and amphoteric surfactants from the viewpoint of improving foamability and foam retention during washing and emulsifying power. In general, a co-surfactant that ionically forms a complex is used together. However, such liquid detergents have problems in stability such as thickening during storage as described in Patent Documents 1 and 2 and formation of precipitates in the composite when stored at low temperature. These publications disclose a technique using a polyoxyalkylene alkyl ether sulfate ester type surfactant having a branched structure.

On the other hand, Patent Document 3 describes that polyoxypropylene alkyl ether sulfate can provide a composition having excellent foaming properties and good low-temperature stability. Patent Document 4 discloses an alkylalkoxylated sulfate to which 0.01 to 30 mol of ethylene oxide and / or propylene oxide is added. Furthermore, Patent Documents 5, 6, and 7 describe a detergent composition containing propylene oxide and a sulfate of alcohol to which ethylene oxide is added. In particular, Patent Document 6 describes a detergent using a polyoxyalkylene alkyl ether sulfate derived from beef tallow-derived higher alcohol or palm oil-derived higher alcohol. Patent Literature 8, Patent Literature 9, and Patent Literature 10 describe a liquid detergent suitable for dishwashing containing an alkylene oxide adduct of a polyhydric alcohol.
JP 2002-194388 A JP 2007-23211 A JP-A-5-97633 Japanese National Patent Publication No. 11-507955 JP 55-84399 A JP-A-56-72092 JP-A-56-5895 JP 63-277300 A Japanese Patent Laid-Open No. 01-292098 Japanese Patent Application Laid-Open No. 06-017095

Recent global warming, such as digitizing the target of CO ₂ emission reduction is imposed, there has been a growing momentum of CO ₂ emission reduction, reduction of the most contribution higher fossil fuel usage CO ₂ emissions And from the idea of carbon neutral, switching to the use of natural raw materials is recommended.

  In this situation, when considering a synthetic surfactant used industrially, a derivative from an alcohol mixture containing about 20% by mass or more of an alcohol of a branched chain alkyl group due to the production method. Or derivatives from secondary alcohols. This is because when alcohol is used as a raw material for a surfactant, the mixture of a surfactant derived from a branched chain alcohol or a secondary alcohol and a surfactant derived from a linear alcohol is mixed with water. This is because it is easy to handle in consideration of the gelation characteristics of the resin, and it is easy to design a stable cleaning agent as compared with the case where it comprises only a surfactant derived from a linear alcohol.

  On the other hand, a surfactant derived from a natural oil / fat raw material (sometimes referred to as “natural raw material” in the present invention), so-called natural surfactant, is composed of a saturated or unsaturated linear hydrocarbon group. In the case of using a natural surfactant as a main base, it is difficult to maintain storage stability at a low temperature. In particular, when the concentration of a surfactant such as a dishwashing agent is high and the surfactants interact with each other to form a complex, the storage stability is significantly impaired.

  Therefore, in the present invention, in a detergent having a high surfactant concentration such as a dishwashing agent, even when natural fats and oils are used as a raw material for all or most of the surfactant, that is, the alkyl group branching ratio is roughly Even when a synthetic surfactant of 20% by mass or more or a nonionic surfactant derived from a secondary alcohol is not substantially used, it has excellent detergency and has no problem in storage stability and gelation characteristics at low temperatures. An object is to provide a liquid detergent composition.

  Another object of the present invention is to provide a liquid detergent composition that is excellent in viscosity adjusting action and / or suppression of surface film formation due to evaporation during storage.

  The present inventors sometimes refer to a polyoxyethylene alkyl ether sulfate ester salt or a polyoxyethylene alkenyl ether sulfate ester type surfactant (hereinafter referred to as “AES”) having a linear hydrocarbon group derived from a natural raw material. Further, the cleaning behavior of AES was examined in detail for the purpose of applying “alkenyl” to “alkyl” in some cases.

  As a result, when used in combination with a surfactant that ionically forms a complex with component (a) such as an amine oxide surfactant (hereinafter sometimes referred to as “AO”), It has been found that AES having a structure in which 1 to 5 moles, particularly 1 to 3 moles of ethylene oxide is added exhibits excellent detergency, while regarding stability, a larger number of moles of added ethylene oxide is superior.

  Furthermore, the present inventors derived from synthetic alcohol rather than AES having a linear hydrocarbon group derived from a natural raw material, particularly a saturated linear hydrocarbon group, that is, a linear alkyl group, in terms of stability. The AES was found to be superior in stability, and as a reason for this, attention was paid to the difference in hydrocarbon groups, particularly alkyl groups.

  As a result of intensive studies, the inventors of the present invention produced a linear hydrocarbon group derived from a natural raw material by first adding a small amount of propylene oxide to alcohol in the production of oxyethylene alkyl ether sulfate (AES). It has been found that the stability of the surfactant possessed can be maintained. The reason is that by adding propylene oxide to the alcohol, a methyl group branch of the oxypropylene group occurs, and a hydrocarbon group having a bulky structure similar to the branched chain of the synthetic alcohol is obtained. It was considered that the packing property can be loosened moderately, and as a result, the stability at low temperatures can be maintained. Further, the present inventors have found that by using the AES, a surfactant having a linear hydrocarbon group, particularly a surfactant derived from a natural raw material can be used as another surfactant. From the above, the present invention has excellent detergency and storage stability with regard to a liquid detergent containing a main chain surfactant having a linear hydrocarbon group, particularly a natural surfactant. It came to be completed.

That is, the present invention provides a means for solving the problems,
(A) 5 to 30% by mass of a compound represented by the compound of the following general formula (1),
(B) 1 to 20% by mass of a surfactant that can form an ionically complex with the component (a) and has at least one linear hydrocarbon group having 8 to 18 carbon atoms,
(C) A surfactant other than component (a) and component (b) having at least one straight-chain hydrocarbon group having 8 to 18 carbon atoms, if desired,
(D) one or more selected from hydrotropes and organic solvents,
And a liquid detergent composition containing water.
R ^a1 O— (PO) _m1 — (EO) _n1 SO ₃ M (1)
[Where,
R ^a1 is a linear hydrocarbon group having 8 to 18 carbon atoms,
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m1 is the average number of moles of PO added and is a number from 0.1 to 1,
n1 is an average addition mole number of EO, and shows a number of 0.5-3.
M is a cation.

in particular,
(A) 5 to 30% by mass of a compound represented by the compound of the following general formula (1),
(B) 1 to 20% by mass of a surfactant that can form an ionically complex with the component (a) and has at least one linear hydrocarbon group having 8 to 18 carbon atoms,
(C) A surfactant other than component (a) and component (b) having at least one straight-chain hydrocarbon group having 8 to 18 carbon atoms, if desired,
(D) one or more selected from hydrotropes and organic solvents,
In addition, the straight chain hydrocarbon group having 8 to 18 carbon atoms in the molecule of the components (a) to (c) has an even number of carbon atoms including a carbonyl group. A liquid detergent composition is provided.
_{^{R a1 O- (PO) m1 -}} (EO) n1 SO 3 M (1)
[Where,
R ^a1 is a linear hydrocarbon group having 8 to 18 carbon atoms,
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m1 is the average number of moles of PO added and is a number from 0.1 to 1,
n1 is an average addition mole number of EO, and shows a number of 0.5-3.
M is a cation.

  Moreover, this invention provides the liquid detergent composition containing 1 or more types chosen from the polypropylene oxide and the ethylene oxide addition product of glycerol as an organic solvent of (d) component of the said invention as a solution of another subject. .

<(A) component>
(A) component of this invention is a compound shown by the compound of the following general formula (1).

R ^a1 O— (PO) _m1 — (EO) _n1 SO ₃ M (1)
[Where,
R ^a1 is a linear hydrocarbon group having 8 to 18 carbon atoms, preferably a linear hydrocarbon group having 8 to 16 carbon atoms, more preferably a linear alkyl group having 10 to 16 carbon atoms, particularly preferably A linear alkyl group having 12 to 16 carbon atoms,
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m1 is the average number of moles of PO added, and is a number of 0.1 to 1, from the viewpoint of storage stability at low temperature, 0.1 or more, preferably 0.2 or more, 1 or less, preferably 0.8. Below, more preferably 0.6 or less.

  N1 is an average added mole number of EO of 0.5 to 3, and is 0.5 or more, preferably 1 or more from the viewpoint of detergency and storage stability, preferably 3 or less from the viewpoint of detergency. Is 2.5, more preferably 2 or less.

  M is a cation, preferably sodium, potassium or magnesium.

In the present invention, the compound of the general formula (1) which is the component (a) may include a straight chain having an even number of carbon atoms of R ^a1 and an odd straight chain, but the component (a) since the naturally occurring fats and oils are preferably those having a hydrocarbon group (hereinafter, sometimes referred to savory), in which case the number of carbon atoms in R ^a1 is even, also is derived from primary alcohol, an oxygen atom Is bonded to the first carbon atom of R ^a1 .

  The component (a) of the present invention can be obtained by the production methods of the following steps (I) to (III).

Step (I): A step of adding propylene oxide to the aliphatic alcohol represented by R ^a1 OH by a known method.

  Step (II): A step of adding ethylene oxide to the propylene oxide adduct obtained in the step (I).

  Step (III): A step of sulfating the ethylene oxide adduct obtained in the above step (II) with sulfur trioxide, chlorosulfonic acid or the like, followed by neutralization.

  The addition reaction requires a catalyst, and an alkali hydroxide such as sodium hydroxide or potassium hydroxide can be used. Moreover, the catalyst which has a magnesium oxide as a main component as described in Unexamined-Japanese-Patent No. 8-323200 can be used. When alkali hydroxide is used, a compound having a relatively wide addition mole distribution of ethylene oxide can be obtained, and when magnesium oxide is used, a compound having a relatively narrow addition mole distribution can be obtained. Further, as disclosed in JP-A-10-158384, it is also possible to control the addition molar distribution by using an alkali catalyst and a metal oxide catalyst in combination.

In step (I), propylene oxide is added to R ^a1 OH, but a proportion of propylene oxide indicated by m1 in general formula (1) is added. The reaction molar ratio of propylene oxide to R ^a1 OH is 0.1 or more, preferably 0.2 or more from the viewpoint of storage stability, and is 1 or less, preferably 0.8 or less, more preferably 0.6 or less. .

The addition reaction is performed using a closed reactor such as an autoclave. First an aliphatic alcohol represented by R ^a1 OH and filled into an autoclave. The catalyst is used in an amount of 0.01 to 5 mol% with respect to the aliphatic alcohol. The catalyst is added to the autoclave, and after sealing, heated to 50 to 150 ° C and dehydrated under reduced pressure. The dehydration time is preferably 0.5 to 2 hours. Subsequently, while maintaining the temperature in the autoclave at 80 to 180 ° C., preferably 100 to 150 ° C., a predetermined amount of propylene oxide is injected into the autoclave using a press-in pump.

  The reaction mole ratio and the number of moles of propylene oxide added are shown in Table 1.

When considering the sulfate ester salt of the component (a) finally obtained, the present inventors preferably reduce the compound having an addition mole number of PO of 2 or more from the viewpoint of stability and detergency. It has been found that the fatty alcohol sulfate salt of the reaction, ie, the alkyl sulfate salt, is preferably reduced in terms of storage stability, and therefore considering the further addition of EO in step (II). The preferred concentration relationship between the unreacted alcohol and the PO adduct after step (I) is:
Unreacted aliphatic alcohol: 30 to 90% by mass, preferably 45 to 80% by mass
PO 1 mol adduct: 10 to 70% by mass, preferably 19 to 50% by mass,
PO 2 mol or more adduct: 0 to 18% by mass, preferably 0 to 10% by mass
It is preferable that

  In addition, the ratio of the compound of Table 1 was measured using the gas chromatography. The column used was a capillary column (DB5 manufactured by Agilent), and the detector was FID.

In the step (II), ethylene oxide is added to the aliphatic alcohol represented by the propylene oxide and R ^a1 OH obtained in the above step (I). The addition ratio is in the general formula (1) per mole of the alcohol. Of ethylene oxide in the proportion indicated by n1.

  When step (II) is a step of further adding ethylene oxide to the propylene oxide adduct obtained in step (I), ethylene oxide is further added to the compound having the propylene oxide addition mole number distribution shown in Table 1. A complex mixture is obtained for the addition.

Specifically, it is a mixture containing the following compounds, particularly a mixture of the following compounds excluding by-products such as polyethylene glycol and polypropylene glycol.
R ^a1 OH (1-1)
R ^a1 O- (PO) _m12 H (1-2)
R ^a1 O— (EO) _n13 H (1-3)
R ^a1 O— (PO) _m12 — (EO) _n14 H (1-4)
[Where,
R ^a1 is the same as described in the general formula (1).
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m12 is the number of moles of PO added and is a number of 1 or more, in particular 1 to 3,
n13 and n14 are the number of moles of EO added and represent a number of 1 or more, particularly 1 to 5].

  The above formula (1-1) and formula (1-3) are obtained from the unaddition products in Table 1, and the formula (1-2) and formula (1-4) are other than those in Table 1. It is obtained from a compound. When adding 0.2 to 0.6 mol of PO in the step (I) and 1 to 2.5 mol of EO in the step (II), the total of the formulas (1-1) to (1-4) The compound of formula (1-1) is 15 to 40% by mass, the compound of formula (1-2) is 5 to 25% by mass, the compound of formula (1-3) is 23 to 60% by mass, and the formula (1- The compound of 4) is 10 to 38% by mass, and the compound of formula (1-3) has the largest content.

  In the case of performing the step (II), a method of continuously injecting ethylene oxide after injecting propylene oxide in the step (I) is suitable from the viewpoint of productivity, and the reaction temperature is 80 to 180 ° C., preferably 100-150 ° C. After completion of the press-fitting, aging is carried out for 0.5-3 hours while keeping the temperature at 80-180 ° C. It can be obtained by neutralizing the alkali catalyst.

  Examples of the sulfation method in step (III) include a method using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid, etc., particularly, waste sulfuric acid and waste hydrochloric acid, etc. From the viewpoint of preventing the generation of sulfur trioxide, a method of continuously supplying sulfur trioxide in a gaseous or liquid state simultaneously with the end of the step (II) is preferable. The reaction temperature is preferably −5 ° C. to 60 ° C., and after contacting sulfur trioxide with the finished product of step (II), it is obtained by aging at −5 ° C. to 60 ° C. for 0.1 to 1 hour. Neutralize sulfur oxides.

  The sulfation is carried out at a ratio of 0.95 to 1.05 mol with respect to 1 mol of alcohol, but is usually carried out at 0.95 to 1.0 mol in order to suppress excessive reaction and coloring. In that case, as a compound that is not sulfated, the formula (1-1) to the formula (1-4) are included in the component (a) in a total of about 3% by mass or less, but when the content is high, It is preferable to reduce the content (preferably to 2% by mass or less) so as not to affect the cleaning power and storage stability. When the content is high, it can be reduced by an operation such as distillation.

  As a method for neutralizing the sulfate, batch type, which performs neutralization while adding and stirring the sulfate to a predetermined amount of neutralizer, and continuously supplying the sulfate and neutralizer into the pipe, stirring and mixing Although the loop type etc. which neutralize with a machine are mentioned, the product of the present invention is not limited to the neutralization method. Examples of the neutralizing agent used here include an aqueous alkali metal solution, aqueous ammonia, and triethanolamine, but an aqueous alkali metal solution is preferred, and sodium hydroxide is more preferred.

The component (a) thus obtained is a propylene oxide adduct of R ^a1 OH, its ethylene oxide adduct, an ethylene oxide adduct of R ^a1 OH, and an unreacted R ^a1 OH addition mole number distribution of each alkylene oxide. Is a sulfate of the mixture having

  The sulfation reactivity of the compound obtained after the step (II) is not substantially changed by the difference in the number of moles of EO or PO within the range specified in the present invention. When 1 to 2.5 mol of EO is added in 2 to 0.6 mol and in step (II), the ratio of the mixed sulfate obtained is the formula (1-1) to formula (1- It becomes the ratio shown in 4). Of course, the ratio of the formula (1-1) to the formula (1-4) remaining as the unsulfurized oxide is also the blending ratio. In addition, since the alkyl sulfate ester salt which is a sulfated unreacted alcohol represented by the formula (1-1) affects low-temperature stability, the formula (1-1) in the alcohol mixture before sulfation is particularly preferred. It is preferable that a compound is 28 mass% or less, Preferably it is 26 mass% or less.

  As described above, the reaction conditions for the sulfation in step (III) are adjusted to such an extent that the washing efficiency and stability are not affected in consideration of the reaction efficiency and the generation of other impurities such as salts caused by excessive reaction. To do.

<(B) component>
The component (b) of the present invention is a surfactant that can ionically form a complex with the component (a) and has at least one linear hydrocarbon group having 8 to 18 carbon atoms. Preferably, the hydrocarbon group bonded to the linear hydrocarbon group having 8 to 18 carbon atoms and the other organic group is a primary carbon atom, more preferably an amine having the primary carbon atom. Oxide type surfactant and / or amphoteric surfactant. Specifically, the compound of the following general formula (2) is suitable.

[Where,
R ^a2 is a hydrocarbon group having a straight chain of 8-18 carbon atoms, preferably 8 to 16 carbon atoms, more preferably a hydrocarbon group having a straight chain of 10 to 16 carbon atoms, especially straight-chain alkyl R ² is preferably a linear alkyl group having 12 and / or 14 carbon atoms when m2 = 0, and a linear alkyl group having 11 and / or 13 carbon atoms when m2 = 1. preferable.

R ^b2 is an ethylene group or a propylene group,
X is a group selected from -COO- and -CONH-.

m2 is a number of 0 or 1, and when m2 = 0 is bonded to R ^a2 −, or X when m2 = 1 is bonded to the first carbon atom of R ^a2 , and R ^c2 and R ^d2 is independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group.

Y is —O ⁻ , —CH ₂ COO ⁻ , —C ₃ H ₆ —SO ₃ ⁻ , —CH ₂ CH (OH) CH ₂ —SO ₃ ⁻ , an alkyl group having 1 to 3 carbon atoms, or 1 to 1 carbon atoms. Selected from 3 hydroxyalkyl groups;
Z ⁻ is an anion.

  n2 is a number of 0 when Y has an anion in the molecule, and a number of 1 when Y is selected from an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. ]

The compound represented by the general formula (2) is known to ionically form a complex with the component (a). As a result, the emulsifying power is improved and the lipophilic stain such as oil stain is prevented. In particular, the detergency can be remarkably improved, in particular, amine oxide in which Y is —O 2 ^— , carbobetaine in which Y is —CH ₂ COO ₂ ^— , and Y is —CH ₂ CH (OH) CH ₂ —SO _3. ^- a suitable sulfobetaine is in terms of emulsifying ability is, Y is -O ^- a is amine oxide is the most preferred compound.

In the present invention, the surfactant having a linear hydrocarbon group having 8 to 18 carbon atoms, which is component (b), has a linear hydrocarbon group having an even number of carbon atoms and a straight chain having an odd number of carbon atoms. The component (b) preferably has a hydrocarbon group derived from natural fats and oils, in which case the carbon number of R ^a2 , provided that when m2 = 1 Carbon number including carbon of carbonyl group in X is an even number, and when m2 = 0, nitrogen atom when m2 = 1 or X when m2 = 1 is bonded to the first carbon atom of R ^a2 become.

In the compound of the general formula (2), a compound in which m2 is 0 can be produced from a tertiary amine represented by R ^a2 —N (R ^c2 ) (R ^d2 ). It can be produced from an aliphatic alcohol represented by R ^a2 —OH as described in Japanese Patent No. 116539, International Publication No. WO2005 / 03512, Japanese Patent Application Laid-Open No. 2007-197396, and the like.

In the compound of the general formula (2), a compound having m2 of 1 is R ^a2 —COX (wherein X is a group selected from OH, OR ′, Cl, Br) and HO—R ^b2 —N (R ^c2 ) ^Obtained by esterification reaction or transesterification reaction with a compound represented by (R ^d2 ), or amidation reaction or aminolysis reaction with a compound represented by H ₂ N—R ^b2 —N (R ^c2 ) (R ^d2 ) Can be prepared from tertiary amines.

In the compounds of formula (2), Y is -O ^- a is amine oxide, it can be produced by reaction of the tertiary amine with hydrogen peroxide, -CH ₂ COO ^- in which carboxymethyl betaine compounds, It can be easily obtained by a reaction between the tertiary amine and V—CH ₂ COOM [V is a chlorine atom or bromine atom, and M is an alkali metal, preferably sodium or potassium].

In the compound of the general formula (2), the compound in which Y is —C ₃ H ₆ —SO ₃ ⁻ and / or —CH ₂ CH (OH) CH ₂ —SO ₃ ^— represents the tertiary amine and V—C ₃ H ₆ —SO ₃ M and / or V—CH ₂ CH (OH) CH ₂ —SO ₃ M [V and M are as defined above] In the case of an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, an alkyl halide having 1 to 3 carbon atoms (preferably alkyl chloride), a dialkyl sulfuric acid having 1 to 3 carbon atoms, ethylene oxide, propylene It can be produced by subjecting the tertiary amine to a quaternization reaction with an alkylating agent such as oxide.

  The reaction is preferably carried out using a solvent in which both the tertiary amine and the compound that reacts with the tertiary amine are uniformly dissolved. For example, water and ethanol, water and isopropanol, water and acetone, etc. are mixed. A solvent etc. can be used conveniently. The reaction temperature varies depending on the compound that reacts with the tertiary amine, but is preferably about 40 to 80 ° C. The molar ratio of the tertiary amine to the compound that reacts with the tertiary amine is 0.9 to 1.3. , Preferably 1.0 to 1.2, particularly preferably 1.01 to 1.2, and an unreacted tertiary amine is reduced by using an equimolar amount or a slight excess of a compound that reacts with a tertiary amine. It is preferable because it can be used.

<(C) component>
If desired, in the present invention, as the component (c), a surfactant having at least one linear hydrocarbon group having 8 to 18 carbon atoms other than the components (a) and (b) can be used. Specific examples of the compound represented by the following general formula (3) include:

R ^a3 -S- [T] _m3 (3)
[Where,
R ^a3 is a linear hydrocarbon group having 8 to 18 carbon atoms, preferably a linear hydrocarbon group having 8 to 16 carbon atoms, more preferably a linear hydrocarbon group having 10 to 16 carbon atoms, particularly a linear alkyl group. There, R ^a3 - S binding and is bound to the first carbon atom of R ^a3, when R ^a3 are bonded -COO- or -CON to <is R ^a2 carbon atoms 11 and / Alternatively, a straight-chain alkyl group having 13 carbon atoms is preferable, and a straight-chain alkyl group having 12 and / or 14 carbon atoms is preferable when bonded to another atom.

  S is a group selected from -O-, -COO-, -N <, and -CON <.

T is a residue obtained by removing a hydrogen atom from a hydroxyl group bonded to R ^a3 _from- (R ^b3 O) _n3 -R ^3c and / or glucose having an average degree of condensation of 1 to 2 (in this case, S is limited to -O- Wherein R ^b3 is an ethylene group and / or a propylene group, R ^3c is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n3 is an average added mole number and 3 to 30 Number.),
m3 is a number of 1 when S is -O-, -COO-, and a number of 2 when S is -N <, -CON <.

In the present invention, the surfactant other than (a) component and (b) component having at least one straight chain hydrocarbon group having 8 to 18 carbon atoms as component (c) is a straight chain having an even number of carbon atoms. The hydrocarbon group and the linear hydrocarbon group having an odd number of carbon atoms may be included, but the component (c) preferably has an alkyl group derived from natural fats and oils. The number of carbons of R ^a3 , provided that when the carbon atom in S to which R ^a3 is bonded is a carbon of a carbonyl group, the carbon number including the carbon of the carbonyl group is an even number, and S is the first carbon of R ^a2 It is bonded to an atom.

In the compound of the general formula (3), when T is — (OR ^b3 ) _n3 —OR ^3c , R ^a3 —OH, R ^a3 —COOR ^3c , R ^a3 —NH ₂ , R ^a3 —CON (R ^b3 It can be produced by subjecting an aliphatic alcohol, aliphatic amine, or fatty acid derivative selected from (OH) ₂ to an addition reaction of ethylene oxide and / or propylene oxide.

In the compound of the general formula (3), when T is a residue obtained by removing a hydrogen atom from a hydroxyl group bonded to R ^a3 from glucose having an average degree of condensation of 1 to 2, a fat represented by R ^a3 —OH Group alcohol and glucose can be produced by performing an acetalization reaction using an acid catalyst such as p-toluenesulfonic acid.

  As already described, since a compound having an alkyl group derived from natural fats and oils can be used as a raw material for the surfactant of the present invention, the number of carbon atoms that the components (a) to (c) of the present invention have in the molecule. The straight chain hydrocarbon group having 8 to 18 is preferably one having an even number of carbon atoms including a carbonyl group (that is, the straight chain hydrocarbon group having 8 to 18 carbon atoms has an even number of carbon atoms). And when it has a carbonyl group bonded to a hydrocarbon group, the carbon number when the carbon atom of the carbonyl group is included is an even number).

  The hydrocarbon group derived from natural fats and oils is unsaturated and saturated, and an alkyl group which is a saturated hydrocarbon group is preferred from the viewpoint of detergency. (A) Component to (c) The straight chain hydrocarbon group having an even number of carbon atoms including the carbonyl carbon is a carbon number distribution of the hydrocarbon group including the carbonyl carbon obtained from the natural fats and oils that originate from the component. For example, it may have a linear hydrocarbon group derived from coconut oil. Further, before synthesis of the target surfactant, for example, by performing a distillation operation on a compound that is a raw material of a hydrocarbon group such as an aliphatic alcohol or a fatty acid methyl ester derived from fats and oils, a specific carbon number of What used only the hydrocarbon group as a raw material may be used. The raw oil and fat will be described later.

<(D) component>
The liquid detergent composition of the present invention is selected from a hydrotrope (hereinafter sometimes referred to as (d-1) component) and an organic solvent (hereinafter sometimes referred to as (d-2) component) as component (d). Contains one or more. The component (d-1) and the component (d-2) are preferably used in combination.

  The hydrotrope agent (d-1) is preferably an alkylbenzene sulfonate having 1 to 3 alkyl groups having a maximum carbon number of 3 or less, specifically toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, and These sodium, potassium or magnesium salts are good, and p-toluenesulfonic acid is particularly good.

  As the organic solvent (d-2), first, (i) an alcohol having 1 to 3 carbon atoms, (ii) a glycol or glycerin having 2 to 4 carbon atoms, and (iii) a dialkyl having 2 to 4 carbon atoms in an alkylene glycol unit. Or, trialkylene glycol, (iv) monoalkoxy (methoxy, ethoxy, propoxy, butoxy), phenoxy or benzooxy ether of di- or tetraalkylene glycol having 2 to 4 carbon atoms in the alkylene glycol unit.

  Specifically, (i) is ethanol, 2-propanol, (ii) is ethylene glycol, propylene glycol, glycerin, isoprene glycol, (iii) is diethylene glycol, dipropylene glycol, and (iv) is propylene glycol monomethyl. There are ether, propylene glycol monoethyl ether, diglycol monobutyl ether, phenoxyethanol, phenoxytriethylene glycol, and phenoxyisopropanol, and a water-soluble organic solvent selected from these is preferable. In particular, ethanol, propylene glycol, dipropylene glycol, butyl diglycol, phenoxyethanol, phenyl glycol, and phenoxyisopropanol are preferable.

  Moreover, polyalkylene glycol can be used as an organic solvent (d-2). Specifically, the polyalkylene glycol is an alkylene oxide adduct of a polyhydric alcohol. Preferable examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol, and neopentyl glycol, and trihydric or higher alcohols such as glycerin, polyglycerin, trimethylolpropane, pentaerythritol, and sorbitol. As the alkylene oxide, ethylene oxide and propylene oxide are preferable.

  Among the alkylene oxide adducts of polyhydric alcohols used in the present invention, ethylene glycol, propylene glycol or glycerin ethylene oxide or propylene oxide adduct is more preferred, and further obtained from polypropylene glycol and glycerin ethylene oxide adduct 1 It is preferable to use more than one species, particularly polypropylene glycol and ethylene oxide adduct of glycerin in combination.

  Polyalkylene glycol, which is an alkylene oxide adduct of a polyhydric alcohol, is useful as an anti-gelling agent. For example, it contains an anti-gelling polymer described in JP-A-11-513067, particularly polypropylene glycol. Is preferable from the viewpoint of viscosity control and storage stability. Polypropylene glycol preferably has a weight average molecular weight of 600 to 5000, more preferably 1000 to 4000.

  The alkylene oxide adduct of glycerin is effective in suppressing the formation of an active agent film that can be formed at the gas-liquid interface of the cleaning composition. Particularly, an average of 5 to 120, preferably 10 to 50 mol of ethylene oxide is added to glycerin. In particular, it is preferable to use an ethylene oxide adduct of glycerin having a weight average molecular weight of 500 to 4000. In the present invention, a naturally occurring surfactant having a linear hydrocarbon group is used, but by using the component (a), an adduct of alkylene oxides of these polyhydric alcohols as compared with the conventional AES. The effect by can be fully exhibited. The weight average molecular weight of the alkylene oxide adduct of polyhydric alcohol can be determined using a light scattering method, and can be measured with a dynamic light scattering photometer (DLS-8000 series, manufactured by Otsuka Electronics Co., Ltd.).

  By using together the ethylene oxide adduct of polypropylene glycol and glycerin as the organic solvent as the component (d), it is possible to impart both effects of adjusting the viscosity and suppressing film formation on the surface due to evaporation during storage.

<(E) component>
In the composition of the present invention, a metal sequestering agent can be blended as the component (e) as necessary. (E) Component includes citric acid, malic acid, EDTA (ethylenediaminetetraacetic acid), tartaric acid, lactic acid, gluconic acid, aminopolycarboxylic acid in which one or more carboxymethyl groups are bonded to the nitrogen atom of amino acid compound [for example, MGDA (Methyl glycine diacetate)] and salts thereof may be blended. Examples of the salt include sodium, potassium, and alkanolamine, but they may be added as an alkali agent as a separate component.

<Other ingredients>
In the liquid detergent composition of the present invention, as other components, for example, antibacterial / antifungal agents known under the trade names such as proxel and caisson, disinfectants such as zinc salts, silver salts, polylysine, phenoxyethanol, sulfuric acid Water-soluble inorganic salts such as magnesium, reducing agents such as sulfites, antioxidants such as BHT and ascorbic acid, thickening polymers such as xanthan gum, guar gum and carrageenan, polymer dispersing agents such as polyacrylic acid polymers, proteases Further, compounds known to be incorporated into liquid detergents such as enzymes such as amylase and lipase, foaming agents, colorants and fragrances can be incorporated.

<Description of hydrocarbon group having 8 to 18 carbon atoms contained in molecule of components (a) to (c)>
In the liquid detergent composition of the present invention, 80 mol% or more of the hydrocarbon groups having 8 to 18 carbon atoms contained in the molecules of the components (a) to (c) are made from natural fats and oils.

  Here, natural fats and oils are corn oil, cottonseed oil, olive oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, palm oil, palm oil, palm kernel oil and other vegetable oils, beef fat, and pork fat. And animal fats such as fish oil, preferably palm oil, palm oil, palm kernel oil, rapeseed oil and beef tallow.

  The components (a) to (c) of the present invention reduce fatty acids obtained by hydrolyzing these fats and oils, methyl esterified fatty acid methyl esters, for example, according to the method described in JP-A-8-169855. Production of a tertiary amine obtained from an aliphatic alcohol obtained by the method described in JP-A No. 11-116539, WO 2005/03512 International Pamphlet, JP-A 2007-197396, etc. Surfactant.

In particular,
R ^a1 OH which is a raw material of the compound of the general formula (1) of the component (a),
In the compounds of the general formula (2) of the component (b) m2 is a raw material of the compound of ^{0 R a2 -N (R c2)} (R d2),
(B) R ^a2 —COX which is a raw material of the compound of the general formula (2) in which component m2 is 1 [when X is halogen, an acid produced using fatty acid and thionyl chloride, phosphorus pentachloride, etc. Chloride)],
(C) R ^a3 —OH, R ^a3 —COOR ^3c , R ^a3 —NH ₂ , R ^a3 —CON (R ^b3 OH) ₂ which are raw materials of the compound of the general formula (3) of the component
However, it is obtained using the above-mentioned natural fats and oils as raw materials.

The liquid detergent composition of the present invention, R ^a1, R ^a2, relative to the total number of moles of R ^a3, fatty acids obtained from the natural fats and oils, fatty alcohols, R ^a1 obtained an aliphatic amine as a starting material, R ^From the viewpoint of carbon neutral, the number of moles of ^a2 and ^Ra3 is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and particularly 100 mol%. preferable. In the present invention, even when such a natural raw material is used, there is no problem such as low temperature stability, and a liquid detergent composition having a very high detergency against lipophilic soil can be obtained.

<Liquid cleaning composition>
The contents of the components (a) to (c) in the liquid detergent composition of the present invention are as follows:
The mixture of the component (a) is 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 5 to 20% by mass,
(B) A component is 1-20 mass%, Preferably it is 1-15 mass%, More preferably, it is 2-15 mass%,
(C) Although it is a component mix | blended with necessity, it is 1-10 mass%, Preferably it is 1-9 mass%, More preferably, it is 1-8 mass%.

  In addition, (a) component and (b) component have a mass ratio of (a) component / (b) component of 0.6 to 7.0, preferably 0.8 to 5.0, particularly preferably 1.0. By setting it to -3.0, the very high emulsification power and the cleaning power of lipophilic soil can be improved.

  Furthermore, the present invention is effective when the concentration of the surfactant is high. The total amount of the component (a) + the component (b) + the component (c) is preferably 10 to 50% by mass, more preferably 10%. In the case of ˜45 mass%, more preferably 10 to 40 mass%, it is possible to obtain a liquid detergent composition that has excellent storage stability and also has a very high emulsifying power and improved lipophilic soil detergency. .

  The liquid detergent composition of the present invention does not exclude surfactants other than the components (a) to (c), and in a range that can solve the problems of the present invention, a small amount of a synthetic surfactant, More specifically, a surfactant having a synthetic alkyl group may be used in combination. The use of synthetic surfactants not only ensures storage stability at low temperatures, but there are also surfactants that are difficult to synthesize in natural systems, and they can be used together to obtain excellent detergency. there is a possibility. However, the feature of the present invention is that the alkyl group or alkenyl group of the surfactant can be replaced with a natural system. Therefore, if the concentration of the synthetic surfactant is limited from the viewpoint of clarifying the characteristics of the invention, the amount of the surfactant having a synthetic alkyl group is 20% by mass or less in the total surfactant, It is preferably 10% by mass or less, and particularly preferably a liquid detergent composition substantially free (0% by mass).

  The content of the component (d) in the liquid detergent composition of the present invention is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass. As the component (d), when the component (d-1) and the component (d-2) are used in combination, the content of the component (d-1) is preferably 0.5 to 10% by mass, more preferably 1 The content of the component (d-2) is preferably 1 to 30% by mass. More preferably, it is 3-25 mass%, More preferably, it is 3-20 mass%.

  The composition of the present invention may be either an aqueous solution in which the above components are dissolved in water or an emulsified emulsion, but an aqueous solution having a transparent appearance is aesthetically preferred. The water to be used is preferably ion-exchanged water or distilled water from which a metal dissolved in a trace amount is removed, and sterilized water containing about 0.1 to 3 ppm of hypochlorite or the like is preferable. The amount of water used in the present invention is the balance (amount to be 100% by mass in total), preferably 85% by mass or less in the composition, and more preferably 80 to 30% by mass when considering other components.

  The pH at 20 ° C. of the liquid detergent composition of the present invention is preferably 4.5 to 9, more preferably 5.5 to 8, and further preferably 5.5 to 7. In the case of adjusting the pH to an acidic value, a chelating agent such as citric acid may be used in addition to an inorganic acid such as hydrochloric acid and sulfuric acid. An oxide may be used. In addition, pH is measured by the method of an Example.

  The viscosity at 20 ° C. of the liquid detergent composition of the present invention is 10 to 1000 mPa · s, preferably 10 to 500 mPa · s, particularly preferably 25 to 500 mPa · s, from the viewpoint of liquid dischargeability. The viscosity is measured with a Brookfield viscometer at 20 ° C. The rotor is no. No. 2 is used and rotated at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the liquid detergent composition.

  The liquid detergent composition of the present invention is suitable for well-known various hard surfaces, particularly for dishwashing used when a user hands wash.

Examples 1-9 and Comparative Examples 1-2
A liquid detergent composition was prepared using the following components (a), (b), (c), etc., and the components shown in Table 3. At that time, the pH was adjusted using 48% sodium hydroxide (shown as “+” in Table 3). The measuring method of pH is as follows. After the adjustment, the detergency and storage stability at low temperatures of these compositions were evaluated by the following methods. The results are also shown in Table 3.

<(A) component>
ES1: 0.4 mol of propylene oxide and 1.5 mol of ethylene oxide were added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide. Neutralized with sodium hydroxide (10% diluted with water until neutralized to pH 11).
ES2: 0.6 mol of propylene oxide and 1.5 mol of ethylene oxide were added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide. Neutralized with sodium hydroxide (10% diluted with water until neutralized to pH 11).
ES3: 1.0 mol of propylene oxide and 1.5 mol of ethylene oxide were added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide. Neutralized with sodium hydroxide (10% diluted with water until neutralized to pH 11).
ES4: 0.2 mol of propylene oxide and 1.5 mol of ethylene oxide were added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide. Neutralized with sodium hydroxide (10% diluted with water until neutralized to pH 11).
ES5: Addition of 0.4 mol of propylene oxide and 2.0 mol of ethylene oxide to a natural alcohol having an alkyl chain of C ₁₂ , followed by sulfation with sulfur trioxide and neutralization with sodium hydroxide (10 with water) % Neutralized until pH was 11).
ES6: 2.0 mol of ethylene oxide was added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide and neutralized with sodium hydroxide (water Neutralized until the pH was 11).
ES7: After 4.0 moles of ethylene oxide was added to natural alcohol with C ₁₂ alkyl chain, it was sulfated with sulfur trioxide and neutralized with sodium hydroxide (pH of 11 diluted with water was 11) Neutralized).

  Details of ES1 to ES7 are shown in Table 2. In addition, said natural alcohol is comprised only with the compound which has a linear alkyl group. The proportion of unsulfurized oxide in each ES component was 1.5% by mass.

In addition, the composition of the unsulfurized oxide of ES1 and ES2 is
In the compound represented by the formula (1-1), ES1 is 24% by mass, ES2 is 20% by mass,
In the compound represented by the formula (1-2), ES1 is 14% by mass, ES2 is 19% by mass,
In the compound represented by the formula (1-3), ES1 is 39% by mass, ES2 is 32% by mass,
In the compound represented by the formula (1-4), ES1 was 29% by mass and ES2 was 23% by mass.

<(B) component>
AO1: N-lauryl-N, N-dimethylamine oxide (the alkyl group is a straight chain derived from nature)
AO2: N-decyl-N, N-dimethylamine oxide / N-myristyl-N, N-dimethylamine oxide = 2/3 (mass ratio) (the alkyl group is a naturally derived straight chain)
APAO: lauramidopropyl-N, N-dimethylamine oxide (the alkyl group is a naturally derived straight chain)
・ Sulfobetaine: Lauryldimethylsulfobetaine (The alkyl group is a straight chain derived from nature)
<(C) component>
AG: The alkyl group is a naturally occurring straight chain, and the alkyl group has a composition of C ₁₂ / C ₁₄ = 60/40 (mass ratio). ) Ingredients>
(D-1) component PTS: p-toluenesulfonic acid (d-2) component EtOH: ethanol PG: propylene glycol PPP: polypropylene glycol having a weight average molecular weight of 1000 <Others>
Preservative: Proxel BDN (1,2-benzisothiazolin-3-one; manufactured by Avisia Corporation).

<Measurement method of pH>
A pH measuring composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution. Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 ml beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01. A sample (liquid detergent composition) was filled in a 100 ml beaker and adjusted to 25 ° C. in a constant temperature bath at 25 ° C. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured.

<Storage stability at low temperature>
100 ml of the liquid detergent composition shown in Table 3 was put into a PET bottle (Takemoto Container Co., Ltd., PEM-100), stored at -5 ° C for 20 days, and the change in the appearance of the liquid was transparent and uniform immediately after preparation. The evaluation was made according to the following criteria in comparison with the normal state.
○: No change in appearance ×: Changes in appearance such as gelation, separation, precipitate formation, etc. <Detergency test>
1 g of model oil stain in which 0.1% by weight of pigment (stan red) is uniformly mixed with rapeseed oil and a polypropylene plate (C-39 PP meat plate made by Kanto Plastic Industry Co., Ltd.) Model contaminated tableware. Commercially available sponges (manufactured by Sumitomo 3M: Scotch Bright) were impregnated with 1.0 g of the liquid detergent composition shown in Table 3 and 30 g of tap water and bubbled by hand 2-3 times. Using this, the model-contaminated tableware was scrubbed and washed, and the number of dishes that could be washed (confirmed whether or not the tableware was washed with or without the sliminess caused by oil stains remaining on the tableware) was determined.

  The viscosity at 20 ° C. of the compositions of Examples 1 to 9 was in the range of 25 to 150 mPa · s.

Examples 10-11
The liquid detergent composition shown in Table 4 containing polypropylene glycol and an ethylene oxide adduct of glycerin as the polyalkylene glycol compound was prepared. The detergency was determined by the above evaluation method. Moreover, the following evaluation method was used about the film formation suppression by storage preservation | save.

<Inhibition of film formation>
250 ml of the liquid detergent compositions of Examples 10 to 11 were placed in a 300 ml beaker and examined for the presence or absence of film formation on the surface after storage for 5 days at 20 ° C. and 65% RH without capping. The case where the film is not formed is marked with ◯, and the case where it is made is marked with X.

The details of each component used are as follows, and the same display as in Table 3 indicates the same as described above.
<(C) component>
-Polypropylene glycol: with a weight average molecular weight of 1000-PET: EO adduct of glycerin (with a weight average molecular weight of 1000)
<(D) component>
-Paratoluenesulfonic acid: Sodium paratoluenesulfonate <Others>
Nonionic-I: Alkyl glucoside having an alkyl group composition of 12/14 carbon atoms = 60/40 (molar ratio) mixed alkyl and an average glucoside condensation degree of 1.5 Nonionic-II: 12/13 mixed carbon atoms An average of 7 moles of EO added to an alkyl secondary alcohol (Softanol 70, Nippon Shokubai Co., Ltd.).

Claims (6)

(A) 5 to 30% by mass of a compound represented by the compound of the following general formula (1),
(B) 1 to 20% by mass of a surfactant that can form an ionically complex with the component (a) and has at least one linear hydrocarbon group having 8 to 18 carbon atoms,
(C) A surfactant other than component (a) and component (b) having at least one straight-chain hydrocarbon group having 8 to 18 carbon atoms, if desired,
(D) one or more selected from hydrotropes and organic solvents,
And a liquid detergent composition containing water.
R ^a1 O— (PO) _m1 — (EO) _n1 SO ₃ M (1)
[Where,
R ^a1 is a linear hydrocarbon group having 8 to 18 carbon atoms,
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m1 is the average number of moles of PO added and is a number from 0.1 to 1,
n1 is an average addition mole number of EO, and shows a number of 0.5-3.
M is a cation. ] (A) 5 to 30% by mass of a compound represented by the compound of the following general formula (1),
(B) 1 to 20% by mass of a surfactant that can form an ionically complex with the component (a) and has at least one linear hydrocarbon group having 8 to 18 carbon atoms,
(C) A surfactant other than component (a) and component (b) having at least one straight-chain hydrocarbon group having 8 to 18 carbon atoms, if desired,
(D) one or more selected from hydrotropes and organic solvents,
As well as water,
A liquid detergent composition having an even number of carbon atoms, including when the straight chain hydrocarbon group having 8 to 18 carbon atoms in the molecule of component (a) to component (c) has a carbonyl group.
R ^a1 O— (PO) _m1 — (EO) _n1 SO ₃ M (1)
[Where,
R ^a1 is a hydrocarbon group having a straight chain of 8-18 carbon atoms,
The oxygen atom of R ^a1 O— is bonded to the first carbon atom of R ^a1 ;
PO and EO are an oxypropylene group and an oxyethylene group,
m1 is the average number of moles of PO added and is a number from 0.1 to 1,
n1 is an average addition mole number of EO, and shows a number of 0.5-3.
M is a cation. ] The liquid detergent composition according to claim 1 or 2, wherein the component (b) is a compound of the following general formula (2).

[Where,
R ^a2 is a linear hydrocarbon group having 8 to 18 carbon atoms,
R ^b2 is an ethylene group or a propylene group,
X is a group selected from -COO- and -CONH-.
m2 is a number of 0 or 1, and when m2 = 0 is bonded to R ^a2 −, or X when m2 = 1 is bonded to the first carbon atom of R ^a2 , and R ^c2 and R ^d2 is independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms.
Y is —O ⁻ , —CH ₂ COO ⁻ , —C ₃ H ₆ —SO ₃ ⁻ , —CH ₂ CH (OH) CH ₂ —SO ₃ ⁻ , an alkyl group having 1 to 3 carbon atoms, or 1 to 1 carbon atoms. Selected from 3 hydroxyalkyl groups, Z ^- is an anion.
n2 is a number of 0 when Y has an anion in the molecule, and a number of 1 when Y is selected from an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. It is. ] The liquid detergent composition according to any one of claims 1 to 3, wherein the component (c) is a compound of the following general formula (3).
R ^a3 -S- [T] _m3 (3)
[Where,
R ^a3 is a linear hydrocarbon group having 8 to 18 carbon atoms, S bonded to R ^a3 — is bonded to the first carbon atom of R ^a3 ,
S is a group selected from -O-, -COO-, -N <, and -CON <. T is a residue obtained by removing a hydrogen atom from a hydroxyl group bonded to R ^a3 _from- (R ^b3 O) _n3 -R ^3c and / or glucose having an average degree of condensation of 1 to 2 (in this case, S is limited to -O- Wherein R ^b3 is an ethylene group and / or a propylene group, R ^3c is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n3 is an average added mole number and 3 to 30 Number.),
m3 is a number of 1 when S is —O— or —COO—, and is a number of 2 when S is —N <or —CON <. ]   The content ratio of the surfactant in the composition is 20 to 50% by mass, and the ratio of the components (a) to (c) in the surfactant is 80% by mass or more. The liquid detergent composition according to any one of the preceding claims.   (D) The liquid cleaning composition of any one of Claims 1-5 containing 1 or more types chosen from the ethylene oxide adduct of polypropylene glycol and glycerol as an organic solvent of a component.