JP5686638B2 - Liquid detergent composition for clothing - Google Patents

Description

  The present invention relates to a liquid cleaning composition for clothing having excellent cleaning performance and stability and solubility in water, and further relates to a liquid cleaning composition for clothing for use by diluting in water.

  In recent years, global energy problems, carbon dioxide emission problems, drought problems, and the like have become serious, and environmental awareness has increased. Under such circumstances, liquid detergents for clothing and residential use have been eagerly desired to appear as detergents that have less burden on the environment. It is conceivable to increase the naturalization rate of so-called concentrated cleaning agents and base materials having higher cleaning component concentrations than conventional cleaning agents. Concentrated type cleaning agents are considered to be very effective in reducing the environmental burden such as reducing the size of the cleaning agent itself, reducing the amount of resin in containers, reducing transportation costs, and reducing waste after use. It is done. In addition, by increasing the naturalization rate of the base material of the surfactant, the dependence on fossil fuels can be reduced, and a cleaner closer to carbon neutral can be obtained.

  However, in a normal liquid cleaning agent, when the concentration of the surfactant, which is a cleaning component, is increased, thickening or gelation occurs, and there is a problem that the usability is remarkably impaired or solidifies during low-temperature storage. In general, as a method for obtaining a composition having a low viscosity and excellent storage stability at a low temperature, it is considered effective to add a large amount of a solvent, a solubilizer and the like.

  Patent Document 1 describes a concentrated liquid detergent composition in which a nonionic surfactant obtained by adding ethylene oxide or propylene oxide to a higher alcohol and a specific solvent are blended. After the addition reaction, ethylene oxide becomes an ethyleneoxy group (hereinafter expressed as EO or may be expressed as an EO group), and propylene oxide is a propyleneoxy group (hereinafter expressed as PO as a general formula). Or may be expressed as a PO group). As a preferable nonionic surfactant in the text and examples, an ethylene oxide-propylene oxide block type nonionic surfactant is described in which ethylene oxide is added and then propylene oxide is added.

  In Patent Document 2, it is represented by RO- (EO) x- (PO) y- (EO) x'-H, and (EO) x, (PO) y, and (EO) x 'are block-bonded in this order. The surfactant composition containing a nonionic surfactant (hereinafter, this type of nonionic surfactant is referred to as “R-EPE nonion” for the sake of convenience) has a high concentration and good handleability. Further, Patent Document 2 discloses a liquid detergent composition containing the surfactant.

  Similarly, Patent Document 3 contains a surfactant composition having a high concentration and good handling properties containing R-EPE nonion and anionic surfactant at a ratio of 99/1 to 10/90, and the surfactant. A liquid detergent composition is disclosed. The use as a cleaning agent for clothing is also described.

  Patent Document 4 discloses a surfactant composition containing R-EPE nonion and a solvent, and a liquid detergent composition using the same, and also describes use as a detergent for clothing.

  Patent Document 5 discloses a laundry detergent containing R-EPE nonion at 10 to 50% by mass and excellent in stability.

  Patent Document 6 and Patent Document 7 disclose a liquid detergent containing R-EPE nonion, an anionic surfactant and other components.

  Patent Document 8 discloses a detergent composition containing a surfactant of a polyoxyalkylene alkyl ether sulfate ester salt having a propyleneoxy group and an ethyleneoxy group, and has a rinsing property containing the surfactant. An excellent heavy or light detergent is suggested. Patent Document 9 and Patent Document 10 disclose polyoxyalkylene alkyl ether sulfate ester surfactants having a propyleneoxy group and an ethyleneoxy group in order to increase the naturalization rate. Although mainly used for tableware, a detergent composition containing a surfactant of a polyoxyalkylene alkyl ether sulfate having a propyleneoxy group and an ethyleneoxy group and a nonionic surfactant is disclosed.

JP-A-8-157867 International Publication No. 1998/024864 Pamphlet International Publication No. 1998/024865 Pamphlet International Publication No. 1998/024867 Pamphlet JP-A-10-195499 JP-A-11-310800 JP-A-11-315299 JP 55-84399 A JP 2009-35726 A JP 2009-185252 A

  In liquid detergents containing water, increasing the concentration of the surfactant, which is a detergent component, causes thickening and gelation (including solidification), and there is a problem that the usability is significantly impaired. In order to solve the problem of a high concentration of activator, a method of obtaining a low viscosity composition by blending a large amount of a solvent, a solubilizing agent or the like can be considered.

  However, even if the cleaning agent has a viscosity reduced by a solvent or a solubilizing agent, when the cleaning agent is diluted with water, particularly cold water, when the cleaning agent is used, the diluted cleaning agent becomes a liquid crystal. If there is a problem with solubility and stability, for example, if the surfactant concentration increases and the surfactant concentration increases, the cleaning agent becomes easier to solidify due to crystal formation during low-temperature storage. In addition, it was found that there is a problem that the cleaning agent itself solidifies when stored at a lower temperature, such as outdoors or in an environment close to it, although it appears to be fluid in the room (about 20 ° C.). The former problem may cause the detergent to remain in the detergent inlet, or if it is directly put into the washing machine, it may cause a poor solubility between the laundry. The latter problem prevents usability.

  While it is desired to improve the cleaning power, which is an essential performance as a liquid cleaning agent, and to solve these problems, Patent Documents 1 to 10 disclose surfactants optimized from this viewpoint. There is no description suggesting the structure or combination of. For example, Patent Document 1 does not mention the relationship between the improvement of the detergency and the surfactant. Although Patent Document 1 mentions low-temperature solubility, according to the evaluation means, the solubility is evaluated by adding a liquid detergent to a large amount of water and stirring, and the stirring conditions are described. Therefore, it cannot be said that sufficient studies have been made, and the actually disclosed composition is not sufficient in low-temperature solubility. Further, Patent Documents 4 to 7 use R-EPE nonion and disclose a surfactant composition having a high concentration and stability. However, these prior arts specifically show examples of ethyleneoxy. The average added mole number of the group is small, and it does not specifically disclose the liquid detergent composition containing the surfactant at a high concentration and the effect thereof.

  On the other hand, Patent Documents 8 to 10 disclose prior art that describes the use of a polyoxyalkylene alkyl ether sulfate ester salt having a propyleneoxy group (PO group) and an ethyleneoxy group (EO group) as a cleaning agent. Yes. Patent Document 8 does not consider the increase in the concentration of the surfactant. The disclosure of Patent Document 9 is limited to the characteristic properties of surfactants. In addition, Patent Document 10 suggests the combined use with polyoxyethylene alkyl ether, but it is mainly used for tableware and there is a description about stability, but in relation to gelation at the time of dilution, polyoxyethylene alkyl ether It does not consider the number of moles of ethylene oxide added.

  An object of the present invention is to provide a liquid cleaning composition for clothing that is excellent in detergency and low-temperature storage stability, and does not have a decrease in solubility due to gel formation when the composition is diluted with water. Providing an agent composition. The term “for clothing” as used herein refers to clothing for textiles, such as clothes, towels, and sheets that can be washed with water for home use or business use. Textile products that used to be dry-cleaned can now be washed with water, and of course these are included. In addition, the target dirt adheres externally or internally in human life activities. Specifically, in addition to mud, dust, carbon, food, oil, etc., sebum, salts and the like can be mentioned. it can. These may mix and adhere.

This invention is the liquid cleaning composition for clothing containing the following (a)-(c) component, Comprising: The sum total of content of (a) component and (b) component is (a) + (b) = It is 30-90 mass%, It is related with the liquid detergent composition for clothes whose mass ratio of (a) component and (b) component is (a) / (b) = 25 / 75-95 / 5.
(A) Component: Nonionic surfactant represented by the following general formula (1) R ¹ O— (A ¹ O) _m H (1)
[In the formula, R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 5 carbon atoms, m represents an average number of added moles, and is a number of 16 to 35. is there. A ¹ O contains an ethyleneoxy group in an average of 14 moles or more. However, when all of A ¹ O are ethyleneoxy groups, m is a number of 18 or more. ]
Component (b): the following general formula (2) anionic surface active agent R ² O-(A ² O) represented by _{p - (EO) q -SO 3} M (2)
[Wherein R ² represents a hydrocarbon group having 8 to 22 carbon atoms, A ² O represents an alkyleneoxy group having 3 and / or 4 carbon atoms, EO represents an ethyleneoxy group, and p and q represent average addition moles. P is a number from 0.1 to 5, and q is a number from 0 to 10. M is a cation. ]
(C) Component: 5-40 mass% of water miscible organic solvent

  The liquid detergent composition for clothing of the present invention is excellent in stability, particularly storage stability at low temperatures, excellent in solubility, particularly in cold water, and excellent in cleaning performance.

<(A) component>
The nonionic surfactant of component (a) used in the present invention is represented by the following general formula (1).
R ¹ O— (A ¹ O) _m H (1)
[In the formula, R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 5 carbon atoms, m represents an average number of added moles, and is a number of 16 to 35. is there. A ¹ O contains an ethyleneoxy group in an average of 14 moles or more. However, when all of A ¹ O are ethyleneoxy groups, m is a number of 18 or more. ]

In general formula (1) of the component (a), R ¹ is a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrocarbon group having 10 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms. R ¹ is preferably a linear hydrocarbon group from the viewpoint of detergency. The hydrocarbon group for R ¹ is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ¹ is preferably a linear or branched group, and more preferably a linear group. Therefore, R ¹ is preferably a linear alkyl group having 8 to 22 carbon atoms. The carbon atom of R ¹ bonded to O of R ¹ O— is preferably a primary carbon atom. When the alcohol before the alkylene oxide is reacted is an aliphatic alcohol derived from natural fats and oils, the obtained component (a) is generally an alkyl group containing the above-mentioned primary carbon atom and the above-mentioned linear alkyl group. Have Use of natural fat-derived alcohol is also preferable from the viewpoint of carbon neutrality.

  Although the method of obtaining the compound of General formula (1) is not specifically limited, It can obtain by adding a C2-C5 alkylene oxide to a C8-C22 alcohol. In the present invention, ethylene oxide is always used as the alkylene oxide.

Here, the average addition mole number m of C2-C5 alkylene oxide is 16-35. When m is 16 or more, it is possible to suppress a decrease in solubility by forming a liquid crystal when diluted with water. Moreover, if m is 35 or less, the stability of the composition will be good. m is preferably 17 or more, more preferably 18 or more, and most preferably more than 18. Further, it is preferably 30 or less, and more preferably 25 or less. In addition, the compound represented by the general formula (1) has an average of 14 mol or more, preferably an average of 15 mol or more, more preferably an average of 16 mol or more, most preferably an ethyleneoxy group which is an alkyleneoxy group having 2 carbon atoms as A ¹ O. Includes 18 or more. All of A ¹ O may be an ethyleneoxy group, in which case m is 18 or more. A ¹ O other than EO is preferably a propyleneoxy group (sometimes referred to as an oxypropane-1,2-diyl group). In general, m may be a reaction ratio of an alkylene oxide having 2 to 5 carbon atoms with respect to an alcohol represented by R ¹ OH during the production of the component (a). Incidentally compound having an alkyleneoxy group having 3 to 5 carbon atoms as A ¹ O are all excellent in high concentration than that of ethyleneoxy groups, easy to maintain stability.

From the viewpoint of detergency, component (a) is composed of (a) component, and the proportion of the compound in which the number of added moles of A ¹ O group is 0 to 5 among the individual compounds constituting component (a) The proportion of the compound which is 0 to 6 mol% in all the constituting compounds and the added mole number of the A ¹ O group is 50 or more (preferably 70 or less from the measurement conditions etc.) constitutes the component (a). It is preferable that it is 0-5 mol% of all the compounds currently performed.

From the viewpoint of solubility and low-temperature stability, the component (a) preferably has a propyleneoxy group as A ¹ O, and the component (a) is a compound represented by the following general formula (1-1). Preferably there is.
_{^{R 1 O - [(C 2}} H 4 O) m1 / (A 1 'O) m2] H (1-1)
[Wherein, R ¹ has the same meaning as described above, and A ^{1 ′} O represents an alkyleneoxy group having 3 to 5 carbon atoms. m1 and m2 are average added mole numbers, m1 is a number of 15 to 30, and m2 is a number of 1 to 5. “/” Indicates that the C ₂ H ₄ O group and the A ^{1 ′} O group may be bonded to either random or block. ]

  The compound of the general formula (1-1) can be obtained by subjecting an alcohol having 8 to 22 carbon atoms to random or block addition reaction of ethylene oxide and an alkylene oxide having 3 to 5 carbon atoms.

  Moreover, m1 in General formula (1-1) is the average addition mole number of the ethyleneoxy group which is EO, and a lower limit is 15 or more from the point of storage stability, solubility, and washing | cleaning performance, Preferably it is 16 or more More preferably, it is 18 or more, and the upper limit is 30 or less, preferably 27 or less, more preferably 24 or less. m2 is the average number of added moles of an alkyleneoxy group having 3 to 5 carbon atoms, and the lower limit is 1 or more, preferably 2 or more, and the upper limit is 5 or less, preferably 4 or less, more preferably from the viewpoint of cleaning performance. Is 3 or less. Note that m = m1 + m2 in relation to the general formula (1).

Alkyleneoxy group of the general formula (1-1) A ^{1 '3~5} carbon atoms is O in are those obtained by addition reaction of several 3-5 alkylene oxide carbon, bonded by an addition reaction The moiety preferably has a methyl branched, ethyl branched or propyl branched structure. Further, an alkyleneoxy group having 3 carbon atoms and / or an alkyleneoxy group having 4 carbon atoms are preferable, and specifically, a trimethyleneoxy group, an oxypropane-1,2-diyl group, an oxybutane-1,2-diyl group, Examples thereof include oxybutane-1,3-diyl group, oxybutane-2,3-diyl group, and oxytetramethylene group. In particular, A ^{1 ′} O is preferably an oxypropane-1,2-diyl group (hereinafter, in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group).

  Particularly in the present invention, the average added mole number m1 of ethyleneoxy group is 15 to 27, more preferably 16 to 24, particularly 18 to 22, and the average added mole number m2 of propyleneoxy group which is PO is 1 to 1. 4, more preferably 2 to 4, particularly 2 to 3 is most preferable because a liquid detergent composition having excellent low-temperature storage stability, cold water solubility and washing performance can be obtained.

In the general formula (1-1), “/” represents an ethyleneoxy group (hereinafter sometimes referred to as EO) which is a C ₂ H ₄ O group of the component (a) of the present invention and an A ^{1 ′} O group. It means that the relationship may be either random bond or block bond. A ^{1 ′} O may be divided as a plurality of block bodies.

Examples of the compound represented by the general formula (1-1) include compounds represented by the following general formulas (1-1-1) to (1-1-6).
^{R 1 O- (A 1 'O} ) m2 - (EO) m1 H (1-1-1)
_{^{R 1 O- (EO) m1 -}} (A 1 'O) m2 H (1-1-2)
^{R 1 O - [(EO)} m11 · (A 1 'O) m2] - (EO) m12 H (1-1-3)
_{^{R 1 O- (EO) m11 -}} [(A 1 'O) m2 · (EO) m12] H (1-1-4)
_{^{R 1 O- (EO) m11 -}} (A 1 'O) m2 - (EO) m12 H (1-1-5)
_{^{R 1 O- (EO) m11 -}} [(A 1 'O) m2 · (EO) m13] - (EO) m12 H (1-1-6)
[Wherein, R ¹ , m 1, m 2, EO, A ^{1 ′} O have the above-mentioned meanings, m ¹¹ , m 12, m 13 are average added mole numbers, each of which is not 0, and m 11 + m 12 + m 13 + m 2 = 16 -35, m1 = m11 + m12 + m13. “·” Indicates a random bond. ]

The compounds represented by the general formulas (1-1-1) to (1-1-6) can be prepared by considering the reaction ratio of the alkylene oxide to R ¹ OH and the reaction sequence. In the general formulas (1-1-1) to (1-1-6), the average number of added moles of each alkyleneoxy group is the number of moles of each alkylene oxide used for R ¹ OH during the reaction. The average addition number of moles of alkyleneoxy group of the obtained compound may be sufficient. In addition, m11 and m12 are independently preferably 1 to 20, more preferably m11 is 3 to 20, and m12 is more preferably 1 to 15, particularly m11 is 4 to 15, and m12 is preferably 3 to 15. M13 is preferably from 0.1 to 10. The ranges of m11, m12, and m13 are subordinate to each range condition or preferred range condition of m1 and m2 in the general formula (1-1). In relation to the general formula (1), m = m1 + m2 = m11 + m12 + m13 + m2.

A compound in which the carbon atom of R ¹ bonded to the oxygen atom of R ¹ —O— in the general formula (1-1) is the first carbon atom is preferable because the detergency is superior to the compound having the second carbon atom. . As described above, alcohols derived from natural fats and oils can be used. In this case, R ¹ is a linear alkyl group having a first carbon atom. Moreover, since it is derived from natural fats and oils, the alkyl group may be composed of a substantially even number of carbon atoms. From the viewpoint of storage stability, the compound represented by the general formula (1-1-2), (1-1-4), (1-1-5) or (1-1-6) is preferable. Formula (1-1-5) or (1-1-6) is more preferable, and (1-1-5) is most preferable. In particular, the proportion of the compound in which the alkyleneoxy group having 2 to 5 carbon atoms bonded to R ¹ —O— is an ethyleneoxy group is 75 mol% or more in the compound constituting the component (a), and more preferably 80 mol. % Or more (the upper limit is 100 mol% or less). Such a compound can be obtained by first adding ethylene oxide to an aliphatic alcohol and then removing unreacted alcohol, or first adding ethylene oxide in an amount of 6 mol or more, particularly 8 mol or more. Can do. In addition, m1 in the general formula (1-1-2), or m11 in the general formula (1-1-4), the general formula (1-1-5), or the general formula (1-1-6). A compound having an average added mole number of 6 or more, particularly 8 or more is also suitable.

In order to further enhance the stability, the compound having the structure of -EO-H at the end in the general formula (1-1) is 70 mol% or more, and further 80 mol% or more (the upper limit is 100 mol% or less). Is preferred. If it is above this value, the stability at low temperatures will be excellent. In the production of the general formula (1-1), such a compound is used after completion of the addition reaction step of C 3-5 alkylene oxide, preferably propylene oxide, which is the basis of A ^{1 ′} O. It can be obtained by adding only 6 mol or more, particularly 8 mol or more of ethylene oxide. Moreover, the average added mole number shown by m12 of the general formula (1-1-3), the general formula (1-1-5) or the general formula (1-1-6) is 6 or more, particularly 8 or more. Also suitable are compounds.

In the present invention, in the general formula (1-1), R ¹ is a linear alkyl group having a first carbon atom bonded to an oxygen atom, and the R ¹ —O—EO— or —EO—H Most preferably, the compound satisfies the condition of mol%. In the present invention, the ratio of R ¹ —O—EO— or —EO—H can be determined by quantitative measurement using C ¹³ -NMR.

The component (a) of the present invention includes, for example, alkylene oxide having 3 to 5 carbon atoms and ethylene oxide according to the structure of general formulas (1-1-1) to (1-1-6) with respect to R ¹ OH. It is obtained by reacting. From the target structure, the blending order and conditions may be examined, and the addition reaction may be performed in a block or random manner. Further, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms and ethylene oxide per mole of R ¹ OH is in the range of m in the general formula (1), that is, 16 to 35, and the preferable numerical value is m. The compounds having the same ranges and different structures can have the conditions of m = m1 + m2 = m11 + m12 + m13 + m2, m1 = m11 + m12 + m13 and the preferred ranges described above. In other words, the reaction ratio of the alkylene oxide having 3 to 5 carbon atoms to be added to the aliphatic alcohol and ethylene oxide may be within the numerical range of m, m1 and m2, m11, m12, and m13.

In general, the ratio of each ethylene oxide or propylene oxide added to 1 mol of R ¹ OH and the average number of added moles of alkyleneoxy groups represented by the respective general formulas are substantially the same. However, depending on the production method, it may be different in the present invention.

  The most preferable compound as the component (a) of the present invention has a structure represented by general formula (1-1-5) or (1-1-6), and particularly a structure represented by general formula (a-1-5). . Further, in the general formula (1-1-5), m11 / (m11 + m12) is preferably 0.2 to 0.8.

As the optimum production conditions further narrowing down the range of m11, m12, m13 and m2, a production method having the following steps A to D can be mentioned.
Step A: Addition reaction of ethylene oxide at a ratio of 4 to 14 moles, preferably 8 to 12 moles (the numerical range may be defined as m11 in the above formula) per mole of R ¹ OH .
Step B: Next, 1 to 3 mol of propylene oxide, preferably 2 to 3 mol (the numerical range may be defined as m2 in the above formula) and 0 to 4 mol of ethylene oxide (the numerical range is the above formula) (Which may be defined as m13) in a random or block addition reaction. Particularly preferably, propylene oxide alone is subjected to an addition reaction of 2 to 3 moles (the numerical range may be defined as m2 in the above formula).
Step C: Thereafter, ethylene oxide is again subjected to addition reaction of 4 to 14 mol, preferably 8 to 12 mol (the numerical range may be defined as m12 in the above formula).
Process D: The process for the catalyst used for reaction is performed. For example, when an alkali catalyst is used, it is neutralized with an acid, and when it is a solid catalyst, filtration is performed.

  In the present invention, the component (a) and the component (b) described later include a small amount of unreacted alcohol, a reaction catalyst (for example, potassium hydroxide, metal compound) and an agent for neutralization thereof (for example, acetic acid and lactic acid), And a polyalkylene glycol having an ethyleneoxy group and an alkyleneoxy group having 3 or 4 carbon atoms formed by the presence of water in the reaction system, and (b) may be mixed with a sulfur oxide, but it has an odor. It may exist as long as it does not affect the present invention due to problems such as the above, manufacturing restrictions in consideration of economy and safety, and other various circumstances.

The m, m1, m2, etc. of the present invention can be determined by NMR or liquid chromatographic analysis. The alkyleneoxy group is short, for example, the proportion of ethylene oxide is less than 8 moles per mole of linear primary alcohol. In the case of a compound obtained by addition reaction in step 1, gas chromatographic analysis may be used. Or in the present invention, m, m1 and m2, etc., may be the proportion of alkylene oxide and ethylene oxide R ¹ O-H 3 to 5 carbon atoms is reacted per mole of.

In the liquid cleaning composition for clothing of the present invention, the content of the component (a) is preferably 15 to 75% by mass, more preferably 25 to 60% by mass, particularly 35 to 50% by mass from the viewpoint of cleaning performance. preferable. The component (a) is a nonionic surfactant of the general formula (1-1-1) when all of A ¹ O in the general formula (1) is a nonionic surfactant having an ethyleneoxy group. In some cases, the content in the composition is preferably 40% by mass or less from the viewpoint of stability at low temperatures and solubility when diluted with cold water. Further, when the component (a) is a nonionic surfactant represented by the general formula (1-1-2), the composition is similarly used from the viewpoints of stability at low temperatures and solubility when diluted with cold water. The content is preferably 50% by mass or less.

<(B) component>
As described above, the component (a) uses a base material having the property of suppressing liquid crystal formation due to water dilution, while the increase in oxyethylene group increases the affinity for water, so Since the interaction is reduced, there is a concern that the cleaning power may be reduced. The component (b) not only solves the problem of detergency but also makes it possible to further reduce the liquid crystal or crystallization region of the liquid detergent composition.

The anionic surfactant as the component (b) used in the present invention is a sulfate ester salt represented by the following general formula (2).
^{R 2 O- (A 2 O)} p - (EO) q -SO 3 M (2)
[Wherein R ² represents a hydrocarbon group having 8 to 22 carbon atoms, A ² O represents an alkyleneoxy group having 3 and / or 4 carbon atoms, EO represents an ethyleneoxy group, and p and q represent average addition moles. P is a number from 0.1 to 5, and q is a number from 0 to 10. M is a cation. ]

The hydrocarbon group which is R ² in the general formula (2) is preferably an alkyl group having 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and particularly preferably 12 to 14 carbon atoms. Furthermore, it is preferable that it is a linear alkyl group derived from a natural fat raw material from performance aspects, such as foaming power and emulsification power, and the environmental aspect of carbon neutral. Accordingly, the carbon atom of R ² bonded to O of R ² O— is preferably a primary carbon atom. As described above, the nonionic surfactant of component (a) is also preferably a compound derived from natural fats and oils, and R ^{1 of} component (a) and R ² of component (b) are each derived from natural fats and oils. Can be used. In that case, the alkyl group may be composed of a substantially even number of carbon atoms.

Examples of the alkyleneoxy group having 3 carbon atoms and / or the alkyleneoxy group having 4 carbon atoms which are A ² O in the general formula (2) include an oxytrimethylene group, an oxypropane-1,2-diyl group, and oxybutane-1 , 2-diyl group, oxybutane-1,3-diyl group, oxybutane-2,3-diyl group, oxytetramethylene group, and combinations of two or more thereof. Among these, oxypropane-1,2-diyl group [As described in the component (a), in the present invention, the oxypropane-1,2-diyl group may be a propyleneoxy group or a PO group. ], An oxybutane-1,2-diyl group (hereinafter, in the present invention, this may be an oxybutylene group or a BO group), more preferably an oxypropane-1,2-diyl group (propyleneoxy group). Group) is most preferred.

P in the general formula (2) is the average number of added moles of A ² O and is a number of 0.1 to 5, preferably 0.2 to 4 from the viewpoint of improving the cleaning performance, More preferably, it is 0.4-3, Most preferably, it is 1-3.

  Q in the general formula (2) is an average added mole number of EO, is a number of 0 to 10, and is preferably a number of 0 to 6, more preferably from the viewpoint of improving the softening performance. It is a number from 0 to 3.

  M in the general formula (2) is a cation group that forms a salt, and examples thereof include alkali metal ions, alkaline earth metal ions, ammonium ions, and alkanol ammonium ions.

  Examples of the alkali metal ion include sodium ion, potassium ion and lithium ion, examples of the alkaline earth metal ion include calcium ion, and examples of the alkanol ammonium ion include monoethanolammonium ion and triethanolammonium ion. Is mentioned. Among these, alkali metal ions such as sodium ions and potassium ions or monoethanolammonium ions are preferable, and monoethanolammonium ions are particularly preferable.

  The production method of the anionic surfactant represented by the general formula (2) is not particularly limited. For example, an alcohol having a hydrocarbon group having 8 to 22 carbon atoms, preferably 1 mol of a linear primary aliphatic saturated alcohol having 10 to 14 carbon atoms, an alkylene oxide having 3 and / or 4 carbon atoms, preferably propylene Oxide is added in an amount of 0.1 to 5 mol, preferably 0.2 to 4 mol, more preferably 0.4 to 3 mol, most preferably 1 to 3 mol, and (poly) oxyalkylene alkyl ether (of alkyleneoxy group) is added. A mixture substantially consisting of 3 and / or 4 carbon atoms, preferably a propyleneoxy group) and an unreacted alcohol is obtained, and then ethylene oxide is 0 to 10 mol, preferably 0 to 5 mol, more preferably 1 to 8 mol, most preferably 1.5 to 5 mol is added, and (poly) oxyalkylene [wherein the alkyleneoxy group has 3 carbon atoms and Or 4, preferably an oxypropylene group] a mixture containing (poly) oxyethylene alkyl ether, or (poly) oxyalkylene [provided that the alkyleneoxy group has 3 and / or 4 carbon atoms, preferably an oxypropylene group ] After obtaining a mixture containing an alkyl ether (when ethylene oxide is not added), the mixture is sulfated and neutralized to obtain a mixture of a polyether sulfate ester salt having an alkyleneoxy group or an ethyleneoxy group. it can.

The anionic surfactant (b) is a mixture of sulfate salts represented by the following general formulas (2-1) to (2-4).
R ² O—SO ₃ M (2-1)
^{R 2 O- (A 2 O)} x -SO 3 M (2-2)
_{^{R 2 O- (EO) y -SO}} 3 M (2-3)
^{R 2 O- (A 2 O)} z - (EO) z '-SO 3 M (2-4)

In the general formulas (2-1) to (2-4), x, y, z, and z ′ are each an integer of 1 or more, x and z are integers of 10 or less, and y and z ′ are 20 The following integers. R ² and M are the same as R ² and M in the general formula (2). When q = 0, the resulting compounds are represented by formula (2-1) and formula (2-2).

In the liquid detergent composition for clothes of the present invention, from the viewpoint of detergency, the total content of the component (a) and the component (b) is (a) + (b) = 30 to 90% by mass, 40 -80 mass% is preferable, and 50-70 mass% is especially preferable. The component (a) is a nonionic surfactant of the general formula (1-1-1) when all of A ¹ O in the general formula (1) is a nonionic surfactant having an ethyleneoxy group. In some cases, the upper limit of (a) + (b) is preferably 55% by mass or less from the viewpoint of stability at low temperatures and solubility during dilution with cold water. Moreover, when (a) component is a nonionic surfactant of general formula (1-1-2), from the viewpoint of the stability at low temperature and the solubility at the time of dilution with cold water, (a) The upper limit value of + (b) is more preferably 65% by mass or less. In addition, since the mass of the anionic surfactant of the component (b) varies depending on the molecular weight of the salt, in the present invention, the mass when the acid type, that is, the counter ion is assumed to be a hydrogen atom ion instead of the salt (b ) The mass of the component.

  In the liquid detergent composition for clothing of the present invention, the mass ratio of the component (a) to the component (b) is (a) / (b) = 25/75 from the viewpoint of cleaning performance, solubility, and stability. To 95/5, preferably 25/75 to 90/10, more preferably 50/50 to 80/20, and particularly preferably 60/40 to 80/20. From the viewpoint of detergency, the proportion of the component (a) in the mass ratio is not less than the lower limit and not more than the upper limit from the viewpoints of solubility and stability. By using the component (a) in combination with the component (b), it is possible to increase the detergency of the composition and further increase the solubility by suppressing liquid crystal formation.

<(C) component>
The liquid detergent composition for clothing of the present invention contains 5 to 40% by mass of (c) a water-miscible organic solvent from the viewpoint of improving stability and solubility. The water-miscible organic solvent referred to in the present invention refers to a solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C., that is, a solvent having a degree of dissolution of 50 g / L or more.

  (C) Content of a component is 5-40 mass% in a composition from the point of stability and solubility, 10-35 mass% is preferable, and 10-25 mass% is especially preferable. From the viewpoint of stability and solubility, the mass ratio [(a) + (b)] / (c) of the sum of the components (a) and (b) and the component (c) is 90/10 to 65. / 35 is preferable, 85/15 to 70/30 is more preferable, and 80/20 to 70/30 is still more preferable.

  As the component (c), a water-miscible organic solvent having a hydroxyl group and / or an ether group is preferable in terms of cleaning performance, stability, and solubility.

  Examples of the water-miscible organic solvent include (c1) alkanols such as ethanol, 1-propanol, 2-propanol, and 1-butanol, and (c2) 2 to 2 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol. 6 alkylene glycols, glycerin, (c3) diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, or alkylene having 2 to 4 carbon atoms such as polyethylene glycol or polypropylene glycol having a weight average molecular weight of 400 to 4000 Polyalkylene glycols composed of glycol units, (c4) diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, or 1-ethoxy-2 A (poly) alkylene glycol (mono or di) alkyl ether comprising (poly) alkylene glycol having 2 to 4 carbon atoms such as propanol and an alkanol having 1 to 5 carbon atoms, (c5) 1-methylglycerin ether 2-methylglycerol ether, 1,3-dimethylglycerol ether, 1-ethylglycerol ether, 1,3-diethylglycerol Alkyl, glyceryl ethers having 1 to 8 carbon atoms such as ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, (c6) 2- It has a C2-C3 alkylene glycol unit such as phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, diethylene glycol monobenzyl ether (poly ) Aromatic ethers of alkylene glycols.

  The component (c) is effective as a viscosity modifier and a gelation inhibitor of the composition, and one or more selected from the above categories (c1) to (c6) are used. It is preferable to use a solvent selected from the above (c1) alkanols, (c2) glycols, (c4) alkyl ethers, and (c6) aromatic ethers, and more specifically, ethanol, propylene glycol, diethylene glycol. By using one or more solvents selected from monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether, in particular, by using two or more solvents together, it is possible to effectively adjust the viscosity of the composition and suppress gelation. It is more preferable because it can be achieved. In the present invention, particularly preferred examples include propylene glycol and / or diethylene glycol monobutyl ether.

<(D) component>
The liquid detergent composition for clothing of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of water as the component (d) in terms of improving stability and solubility. It is preferable to use water that does not affect the composition, such as deionized water (sometimes referred to as ion-exchanged water).

<Other ingredients>
[(E) component]
The liquid detergent composition for clothing of the present invention can contain a surfactant other than the component (a) and the component (b) [hereinafter referred to as the component (e)] within a range that does not impair the effects of the present invention. . Examples of the component (e) include the following (e1) to (e4).
(E1) Nonionic surfactants that do not fall under component (a).
For example, the following (e1-1) and (e1-2) are mentioned.
(E1-1) An alkyl polysaccharide surfactant represented by the following general formula.
R ^1e- (OR ^2e ) _X G _Y
[Wherein, R ^1e is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, R ^2e is an alkylene group having 2 to 4 carbon atoms, and G is derived from a reducing sugar having 5 or 6 carbon atoms. Residue, X represents an average value of 0-6, and Y represents an average value of 1-10. ]
(E1-2) Fatty acid alkanolamide, polyhydroxy fatty acid amide.

(E2) Anionic surfactants not corresponding to component (b), particularly alkylbenzene sulfonates, fatty acid salts, alkane sulfonates, alkyl sulfate esters and polyoxyalkylenes having an alkyl group having 8 to 22 carbon atoms Alkyl ether sulfate ester salt. Here, the salt may be the same as M of component (b).

(E3) Cationic surfactant.
For example, it is a primary to tertiary amine having a long-chain alkyl group (excluding alkanolamines described later), and preferably has 8 to 8 carbon atoms which may have an ether bond, an ester bond or an amide bond in the middle. Mention may be made, for example, of cationic surfactants having one or two 22 alkyl groups, the remainder being alkyl groups which may have a hydrogen atom or a hydroxy group having 4 or less carbon atoms. In the present invention, a quaternary ammonium type surfactant having one long-chain alkyl group having 8 to 22 carbon atoms and a tertiary amine having one long-chain alkyl group having 8 to 22 carbon atoms are preferable.

(E4) Amphoteric surfactant For example, sulfobetaine or carbobetaine having an alkyl group having 10 to 18 carbon atoms can be mentioned.

  The content of the component (e) is preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass in the liquid detergent composition for clothing of the present invention. In addition, nonionic surfactant (e1) and anionic surfactant (e2) are combined with said (a) component and (b) component among (e) component, [(a) + (e1)] / [(B) + (e2)] is preferably within the range of the mass ratio of (a) / (b). For the quaternary ammonium salt, the mass excluding the counter anion is the mass of the quaternary ammonium salt, and for the tertiary amine, hydrogen atoms other than organic groups are substituted among the groups bonded to the nitrogen atom. The mass of the resulting structure is defined as the mass of the tertiary amine.

  The alkyl group of the surfactant as the component (e) is preferably derived from natural fats and oils, and more preferably a linear saturated alkyl group. (E) As a component, a fatty acid salt and a C8-C22 fatty acid salt are preferable.

[(F) Alkaline agent]
The liquid detergent composition for clothing of the present invention preferably contains an alkali agent [hereinafter referred to as component (f)]. In addition to alkali metal hydroxide, alkali metal carbonate, and the like, the alkali agent is an alkanol group having 2 to 4 carbon atoms among the groups bonded to the nitrogen atom, and the remainder is 1 to 4 carbon atoms. And an alkanolamine which is an alkyl group or a hydrogen atom. Of these, the alkanol group is preferably a hydroxyalkyl group, more preferably a hydroxyethyl group. Other than the alkanol group, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. As alkanolamine, 2-aminoethanol, N-methylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanol Alkanolamines such as amine and isopropanolamine mixtures (mono, di and tri mixtures) can be mentioned. In the present invention, monoethanolamine and triethanolamine are more preferable, and monoethanolamine is most preferable.

  The component (f) can be used as a pH adjuster described later. Moreover, you may mix | blend as a counter salt of above-mentioned (b) component.

  The liquid detergent composition for clothes of the present invention preferably contains 0.01 to 10% by mass, more preferably 0.5 to 8% by mass of the component (f). Among them, the alkanolamine is preferably contained in the component (f) in an amount of 0.5 to 8% by mass, more preferably 1 to 7% by mass, and further preferably 3 to 6% by mass.

Hereinafter, other components that can be used in the present invention will be shown [component (g)].
The liquid detergent composition for clothing of the present invention can contain a chelating agent [hereinafter referred to as component (g)]. (G) The chelating agent of a component can use the well-known thing used for a liquid detergent, for example,
Aminopolyacetic acid or salts thereof such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, diencoric acid,
Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid and the like, or salts thereof,
Examples thereof include aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and alkali metal or lower amine salts thereof. In the present invention, the alkanolamine mentioned in the component (b) is preferably used as a salt, and may be a salt blended with an acid and neutralized with an alkali agent in the system.

  (G) The mixture ratio in the composition of a component is 0.1-5 mass% when it considers that it is an acid type, Preferably it is 0.1-4 mass%, More preferably, it is 0.1-3 mass%. It is.

[Other ingredients]
Furthermore, the components shown in the following (i) to (xii) can be blended in the liquid detergent composition for clothing of the present invention to such an extent that the effects of the present invention are not impaired.
(I) Polyacrylic acid, polymaleic acid, carboxymethyl cellulose, polyethylene glycol having a weight average molecular weight of 5000 or more, maleic anhydride-diisobutylene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-vinyl acetate copolymer Recontamination preventing agents such as polymers, naphthalene sulfonate formalin condensates, and polymers described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of JP-A-59-62614; Dispersant (ii) Color transfer inhibitor such as polyvinylpyrrolidone (iii) Bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate (iv) Tetraacetylethylenediamine, general formula (I- Bleach activators such as bleach activators represented by 2) to (I-7) (v) cellulase, amylase Enzymes such as pectinase, protease, lipase (vi) Boron compounds, calcium ion sources (calcium ion supply compounds), bihydroxy compounds, formic acid and other enzyme stabilizers (vii) fluorescent dyes such as Tinopearl CBS (trade name, Ciba Fluorescent dyes (viii) butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite, which are commercially available as Specialty Chemicals) and Whiteex SA (trade name, manufactured by Sumitomo Chemical Co.) Solubilizers such as toluene sulfonic acid, cumene sulfonic acid, metaxylene sulfonic acid, benzoate (also effective as preservative) (x) polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, average Polypropylene with a molecular weight of about 2000 Polyalkylene glycol-based anti-gelling polymers such as lenglycol (xi) Paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, halogenation such as methylene chloride and 1,1,1-trichloroethane Water-immiscible organic solvents such as alkyls and terpenes such as D-limonene.
(Xii) Other antifoaming agents such as pigments, fragrances, antibacterial preservatives, and silicones

  In the liquid detergent composition for clothing of the present invention, the concentration as an index in the case of blending the above-mentioned optional components is shown below, but it is appropriately adjusted to the extent that this effect is not impaired, and is excluded when it is not suitable for blending. . The content of the anti-staining agent and dispersant (i) is preferably 0.01 to 10% by mass. The content of the color transfer inhibitor (ii) is preferably 0.01 to 10% by mass. The content of the bleaching agent (iii) is preferably 0.01 to 10% by mass. The content of the bleach activator (vi) is preferably 0.01 to 10% by mass. The content of the enzyme (v) is preferably 0.001 to 2% by mass. The content of the enzyme stabilizer (vi) is preferably 0.001 to 2% by mass. The content of the fluorescent dye (vii) is preferably 0.001 to 1% by mass. The content of the antioxidant (viii) is preferably 0.01 to 2% by mass. The solubilizer of (ix) is preferably 0.1 to 2% by mass. The polyalkylene glycol-based anti-gelling polymer (x) is preferably from 0.01 to 2%. The water immiscible organic solvent (xi) is preferably 0.001 to 2% by mass. The other components of (xii) can be blended at a known concentration, for example.

  Of the above-mentioned optional components, (ix), (x), and (xi) affect the stability of the liquid detergent composition, so that special attention must be paid to their formulation.

  The pH of the liquid detergent composition for clothing of the present invention is measured by the method described in Item 8.3 of JIS K3362: 1998, and the temperature is measured at 20 ° C. described. In view of obtaining excellent cleaning performance, 6 to 11, particularly 8 to 10 is preferable.

  The viscosity at 20 ° C. of the liquid detergent composition for clothing of the present invention is preferably 10 to 500 mPa · s, more preferably 50 to 400 mPa · s, and still more preferably 100 to 300 mPa · s in terms of ease of handling. (C) It is preferable to adjust so that it may become such a range with a component and a solubilizing agent.

  The liquid detergent composition for clothing of the present invention is a composition that does not cause gelation or increase in viscosity when diluted with water. Here, the gelation means a state in which fluidity is lost or in a state in which it cannot be substantially measured in the viscosity measurement using a B-type viscometer described below. Specifically, any liquid detergent composition for clothing having a temperature of 5 to 40 ° C. is diluted with water at 10 ° C., preferably with water at 5 ° C. in a range of more than 0 times to 100 times. It is preferable not to gel.

  When the liquid detergent composition is diluted with water, the effect on the solubility due to gelation or increase in viscosity is that the liquid detergent composition is diluted with ion-exchanged water in a range of 0 to 20 times. It can be judged from the liquidity of a plurality of samples with different values. Specifically, the liquid detergent composition at 25 ° C. and the ion exchange water at 25 ° C. are expressed as [(mass of liquid detergent composition for clothing) / (mass of liquid detergent composition for clothing + ion exchange water). Mass)] x 100 = 5 to 95% by mass. Prepare a total of 19 samples mixed in increments of 5% by mass and judge from the liquidity of the sample after storing the sample at 10 ° C for 1 day. In the evaluation under these conditions, all samples having excellent fluidity are judged to correspond to the viscosity at 10 ° C. of all the samples after storage at 10 ° C. being less than 1500 mPa · s. Furthermore, after 19 samples obtained in the same manner are stored at 5 ° C. for 1 day, all the samples are excellent in fluidity, ie the viscosity at 5 ° C. of all the samples after storage at 5 ° C. The liquid detergent composition for clothing of the present invention is excellent in fluidity at 10 ° C. and further at 5 ° C. under the diluted sample conditions. The temperature of the liquid detergent composition for clothing before dilution mixing and the temperature of ion-exchanged water were 25 ° C., but each temperature before dilution mixing was selected from other temperatures (for example, 15 to 30 ° C.) The same result can be obtained using a liquid detergent composition that causes gelation problems when diluted with water at 10 ° C. The fluidity at 10 ° C. of at least one sample of the sample group diluted under the conditions is in a state of poor fluidity or substantially no fluidity, and it has a viscosity at 10 ° C. of 1500 mPa · s or more, particularly 2000 mPa · s. More than It corresponds to the state where the viscosity is not measured or the viscosity cannot be measured.

  In the present invention, the viscosity is measured with a B-type viscometer. Select a rotor that matches the viscosity. It rotates 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 or diluent. Viscosity measurement temperature (liquid temperature) is selected according to each purpose.

  The liquid detergent composition of the present invention is for clothing and is a composition for washing with water. As described above, the clothing refers to a textile product to be washed using water as a main cleaning medium, such as clothing, towels, and sheets.

  The components shown in Table 1 were mixed to obtain compositions of Examples and Comparative Examples. The following evaluations were performed using the obtained compositions. The results are shown in Table 1.

(1) Detergency evaluation (1-1) Preparation method of cocoon pieces 衿 As a soil test cloth, the ones with the same degree of soiling were selected from those collected by cutting the heel part of a cotton / polyester blended shirt worn for 3 days. . The selected wrinkle stain test cloth was cut in half and sewed one by one on a 30 cm × 30 cm cotton cloth (hereinafter referred to as a scissors), and six sets (12 sheets in total) were prepared for each experiment shown in Table 1. One of the half-cut sheets was used as the detergent shown in the examples, and the other six sheets were used as index detergents for determining the cleaning power.

(1-2) Washing water preparation method To make calcium / magnesium = 8/2 as a hardness component, the water used for washing is calcium chloride dihydrate 25.14 g and magnesium chloride hexahydrate 8. 400 ° DH hard water obtained by dissolving 70 g with 2966.13 g of ion exchange water was used, diluted with ion exchange water at the time of use of the detergency test and adjusted to 4 ° DH.

(1-3) Determination Method For the cleaning test, water prepared by the above method was used using a washing machine (NA-FV8001; Panasonic). Detergency was determined by 10 panelists (male in their 30s). Six pieces of scissors cleaned in the same manner except that six pieces of scissors cleaned with the liquid detergent composition (evaluation detergent) in Table 1 and the indicator detergent described in JIS K 3362: 1998 were used instead of the detergent. The degree of washing was visually judged. Judge which of the pair of pieces is superior in cleaning power, +1 points when the detergent using the evaluation detergent has better cleaning power, and better cleaning power when using the indicator detergent The case is set to “−1” (the total evaluation score per panelist is in the range of “+6” to “−6”). 10 panelists evaluated each evaluation detergent, and the detergency was evaluated based on the average score of the 10 panelists.

(2) Storage stability evaluation A 50 mL sample bottle (No. 6 wide-mouthed standard bottle, made of glass, cylindrical shape with a diameter of 40 mm and a height of 80 mm) was filled with 40 mL of the liquid detergent composition, capped, and then 5 It was left to stand in a constant temperature room at 20 ° C. for 20 days. The stability of the composition was determined by visually observing the appearance and following criteria.
A: A uniform liquid phase in which no liquid crystal or crystals are formed, and the liquid stability is excellent.
X: Liquid crystal formation, crystal formation, separation, or precipitation is observed.

(3) Model evaluation of solubility The liquid detergent composition and ion-exchanged water that have been kept at 25 ° C. (room temperature) are expressed as [(mass of liquid detergent composition) / (mass of liquid detergent composition + ion Mass of exchanged water] × 100 = 5 to 95% by mass A total of 19 samples mixed in increments of 5% by mass were prepared and allowed to stand in a temperature-controlled room at 10 ° C. for 1 day. The viscosity was measured under the following conditions and judged according to the following criteria: This is a solubility model test in water at 10 ° C. Further, for samples whose result at 10 ° C. was “◯”, the same was applied. Then, a solubility model test at 5 ° C. (viscosity was measured at 5 ° C.) was conducted.
○: All samples have excellent fluidity.
X: One or more samples have poor fluidity or substantially no fluidity in the sample.

  Each component described in the table will be described below. In the table, (a′-1) to (a′-3) are also regarded as the component (a), and (b′-1) is also regarded as the component (b). Indicated.

(A) Component (a-1): A block addition reaction of 18 moles of ethylene oxide and 2 moles of propylene oxide per mole of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil. [In General Formula (1-1-2), R ¹ is a primary linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m1 is 18 on average, and m2 is on average The compound of 2 and the compound of R < ¹ > -O-EO were 90 mol% or more. ]
(A-2): Block addition reaction of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide per mole of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil . [In General Formula (1-1-5), R ¹ is a linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m11 is an average of 8, m2 is an average of 2 and Compounds having an average of m12 of 8, of which R ¹ —O—EO compound was 80 mol% or more, and —EO—H compound was 90 mol% or more. ]
(A-3): Block addition reaction of 9 mol of ethylene oxide, 1 mol of propylene oxide and 9 mol of ethylene oxide per 1 mol of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil . [In General Formula (1-1-5), R ¹ is a linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m11 is an average of 9, m2 is an average of 1 and Compounds having an average of m12 of 9, of which R ¹ —O—EO compound was 85 mol% or more, and —EO—H compound was 90 mol% or more. ]
(A-4): Block addition reaction of 9 moles of ethylene oxide, 2 moles of propylene oxide and 9 moles of ethylene oxide per mole of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil . [In General Formula (1-1-5), R ¹ is a linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m11 is 9 on average, m2 is 2 on average, and Compounds having an average of m12 of 9, of which R ¹ —O—EO compound was 85 mol% or more, and —EO—H compound was 90 mol% or more. ]
(A-5): 10 moles of ethylene oxide per mole of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil, an average of 2 moles of propylene oxide, and 10 moles of ethylene oxide in this order. . [In General Formula (1-1-5), R ¹ is a primary linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m11 is 10 on average, and m2 is on average 2 and m12 are average 10 compounds. Of these, the R ¹ —O—EO compound was 90 mol% or more, and the —EO—H compound was 95 mol% or more. ]
(A-6): A product obtained by subjecting 25 moles of ethylene oxide to an addition reaction per mole of primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil. [In the general formula (1), R ¹ is a primary linear alkyl group having 10 to 14 carbon atoms, A ¹ O is an ethyleneoxy group, and m is an average of 25 compounds. ]

(A′-1): An average of 10 moles of ethylene oxide added to a primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil (a′-2): having 10 to 14 carbon atoms derived from coconut oil A primary linear alcohol with an average of 50 moles of ethylene oxide added (a'-3): 5 moles of ethylene oxide and 2 moles of propylene oxide in a primary linear alcohol having 10 to 14 carbon atoms derived from coconut oil And block addition reaction of ethylene oxide in the order of 5 moles. [In General Formula (1-1-5), R ¹ is a primary linear alkyl group having 10 to 14 carbon atoms, A ^{1 ′} O is an oxypropylene group, m11 is 5 on average, and m2 is on average Compounds with an average of 2 and m12. Among these, the R ¹ —O—EO compound was 80 mol% or more, and the —EO—H compound was 85 mol% or more. ]

(B) Component (b-1): An anionic surfactant produced by the following production method (b1) [The concentration in the table is the acid type concentration, and the monoethanolamine as a salt is added to the component (f). did. ]
<Production method (b1)>
A linear primary alcohol having 12 carbon atoms derived from natural fats and oils (trade name: Calcol 2098, manufactured by Kao Corporation) and 3.5 g of KOH were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, 110 ° C., Dehydration was performed at 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, and after raising the temperature to 120 ° C., 1460 g of propane-1,2-diyl oxide (hereinafter referred to as “PO”) was charged. After addition reaction and aging at 120 ° C., cooling to 80 ° C., removing unreacted PO at 4.0 kPa, adding 3.8 g of acetic acid into the autoclave, and stirring at 80 ° C. for 30 minutes The alkoxylate having an average added mole number of PO of 2.0 was obtained.

The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas. The obtained sulfate was neutralized with monoethanolamine to obtain a composition containing polyoxypropane-1,2-diylalkyl ether sulfate ester [(b-1)].

The obtained (b-1) is a compound in which R ² is a linear primary alkyl group, A ² O is a propyleneoxy group, p is 2.0 on average, and q is 0 in the general formula (2) It is. Further, as a result of gas chromatographic analysis and NMR analysis, the obtained composition contains 98% by mass of the compound represented by the general formula (2 ′) and 2% by mass of the compound of the general formula (2-1). It was.

(B-2): Anionic surfactant produced by the following production method (b2) [The concentration in the table is the concentration of the acid type, and the monoethanolamine of the salt was added to the component (f). ]
<Production method (b2)>
In the same manner as in the production method (b1), a linear primary alcohol having 12 carbon atoms (trade name: Calcoal 2098) derived from natural fats and oils was dehydrated. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and then 730 g of PO was charged. After addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 1107 g of ethylene oxide (hereinafter referred to as “EO”) was charged. After addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C., and unreacted EO was removed at 4.0 kPa. After removal of unreacted EO, 3.8 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then extracted. The average PO addition mole number p was 1.0 and the average EO addition mole number q was 2. An alkoxylate of 0 was obtained.

  The resulting alkoxylate was sulfated in the same manner as in production method (b1) and then neutralized to obtain a composition containing an alkyl ether sulfate ester salt [(b-2)].

As a result of gas chromatographic analysis and NMR analysis, the obtained (b-2) is the general formula (2), wherein R ² is a linear primary alkyl group having 12 carbon atoms and A ² O is a propyleneoxy group. , P is an average of 1.0, and q is an average of 2.0. Further, as a result of gas chromatographic analysis and NMR analysis, the obtained composition contained 80% by mass of the compound represented by the general formula (2 ′), 4% by mass of the compound of the general formula (2-1), and the general formula. The compound of (2-3) was contained by 16% by mass.

(B′-1): Anionic surfactant produced by the following production method (b′1) <Production method (b′1)>
The raw material alcohol is an alcohol obtained by hydroformylating a mixture of 1-decene and 1-dodecene [1-decene / 1-dodecene = 50/50 (mass ratio)]. In the same manner as (b-1), an average of 1 mol of ethylene oxide was added to this alcohol, then sulfated with sulfur trioxide, neutralized with sodium hydroxide, and polyoxyethane-1,2-diylalkyl. A composition containing an ether sulfate ester salt [(b′-1)] was obtained. As a result of gas chromatographic analysis and NMR analysis, the obtained (b′-1) was a compound with p = 0 and q = 1.0 outside the range of the general formula (2). Moreover, as a result of the gas chromatograph analysis and the NMR analysis, the obtained composition contains 0% by mass of the compound of the general formula (2 ′), 40% by mass of the compound of the general formula (2-1), and the general formula. 60 mass% of the compound of (2-3) was contained.

(C) Component (c-1): Diethylene glycol monobutyl ether (c-2): Propylene glycol

(E) Component (e1-1): A secondary alcohol having 12 to 14 carbon atoms added with an average of 3 moles of ethylene oxide [Softanol 30 (trade name), manufactured by Nippon Shokubai Co., Ltd.]
(E2-1): Alkylbenzenesulfonic acid having a linear alkyl group having 10 to 14 carbon atoms (e2-2): LUNAC L-55 (trade name) (coconut oil fatty acid; manufactured by Kao Corporation)
(F) Component (f-1): Monoethanolamine (including the concentration of the (b) component and (e2) component as a counter ion)

<Other ingredients>
Polymer (1): a polymer compound synthesized by the method of Synthesis Example 1 in paragraph 0020 of JP-A-10-60476.
Fluorescent dye: Chino Pearl CBS-X (trade name) (manufactured by Ciba Specialty Chemicals)
Enzyme: Everase 16.0L-EX (trade name) (protease, manufactured by Novozyme)
Dye (1): Green No. 202

Claims (6)

A liquid detergent composition for clothing containing the following components (a) to (c), wherein the total content of components (a) and (b) is (a) + (b) = 30 to 90 mass The liquid cleaning composition for clothing, wherein the mass ratio of the component (a) to the component (b) is (a) / (b) = 25/75 to 95/5.
(A) Component: Nonionic surfactant represented by the following general formula (1) R ¹ O— (A ¹ O) _m H (1)
[In the formula, R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, A ¹ O represents an alkyleneoxy group having 2 to 3 carbon atoms, m represents an average number of added moles, and is a number of 16 to 35. is there. A ¹ O contains an ethyleneoxy group in an average of 14 moles or more. However, when all of A ¹ O are ethyleneoxy groups, m is a number of 18 or more. ]
Component (b): the following general formula (2) anionic surface active agent R ² O-(A ² O) represented by _{p - (EO) q -SO 3} M (2)
[Wherein, R ² represents an alkyl group having 12 to 14 carbon atoms, A ² O represents an alkyleneoxy group having 3 and / or 4 carbon atoms, EO represents an ethyleneoxy group, and p and q represent the average number of moles added. P is a number from 0.1 to 3, and q is a number from 0 to 10. M is a cation. ]
(C) Component: 5-40 mass% of water miscible organic solvent The liquid detergent composition for clothes according to claim 1, wherein the component (a) contains a propyleneoxy group as A ¹ O. The liquid detergent composition for clothes according to claim 1 or 2, wherein the component (a) is a compound represented by the following general formula (1-1).
_{^{R 1 O - [(C 2}} H 4 O) m1 / (A 1 'O) m2] H (1-1)
[Wherein, R ¹ represents a hydrocarbon group having 8 to 22 carbon atoms, and A ^{1 ′} O represents an alkyleneoxy group having 3 carbon atoms. m1 and m2 are average added mole numbers, m1 is a number of 15 to 30, and m2 is a number of 1 to 5. “/” Indicates that the C ₂ H ₄ O group and the A ^{1 ′} O group may be bonded to either random or block. ] (B) in the general formula of component (2), the carbon atoms of R ² that bind to the R ² O-O-is a primary carbon atom, laundry liquid cleaning according to any one of claims 1 to 3 Agent composition.   Further, among the groups bonded to the nitrogen atom, 1 to 3 is an alkanolamine having 2 to 4 carbon atoms, and the rest is 0.01 to 10 mass of an alkanolamine having an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. The liquid cleaning composition for clothing according to any one of claims 1 to 4, which is contained in%. The liquid detergent composition for clothes according to any one of claims 1 to 5, wherein the mass ratio of the component (a) to the component (b) is (a) / (b) = 25/75 to 90/10.