KR102182275B1 - Liquid detergent - Google Patents

Abstract

A liquid detergent containing the following (A) component, (B) component, and (C) component, and wherein the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent: ( A) component: A compound represented by the following general formula (a-1) (in the formula, R ¹ is a C9-C13 hydrocarbon group, R ² is a C2-C4 alkylene group, R ³ is a C1-C4 hydrocarbon group, 4 is an alkyl group, and m is a number of 5 to 25), and a compound represented by the following general formula (a-2) (wherein R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, and EO is an oxyethylene group , PO is an oxypropylene group, s is a number of 5 to 20, t is a number of 1 to 4) and a compound represented by the following general formula (a-4) (wherein R ¹ is a C10 A hydrocarbon group of -20; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p>0, q>0, and p+q is a number of 10 or more and less than 60) Nonionic surfactant containing at least one compound selected from the group consisting of; (B) component: a compound represented by the following general formula (b-1) (in the formula, Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group, a+b=7 to 19, c+ d=7-19 and e+f=7-19.) and at least one compound selected from the group consisting of an alcohol having 6 or more and 18 or less carbon atoms; And (C) component: Anionic surfactant;

Description

Liquid detergent {LIQUID DETERGENT}

The present invention relates to a liquid detergent.

This application claims priority based on Japanese Patent Application No. 2013-085808 for which it applied to Japan on April 16, 2013, and uses the content here.

There are a powder type and a liquid type as a detergent used for washing clothes, etc. Since liquid detergents are less likely to melt and can be applied directly to clothes or the like, in recent years, the usage ratio is increasing (refer to Patent Document 1).

The cleaning agent is required to have high cleaning power against contamination adhering to clothing or the like. Among the contamination adhering to clothes, etc., contamination with a high load containing a large amount of solids or oil (for example, sebum contamination) is difficult to fall off, and high cleaning power is required even for such contamination with a high load.

For high-load contamination, it is said that it is effective to apply a liquid detergent directly to the contamination.

In order to improve the coating and cleaning power in the case of washing by directly applying a liquid detergent to contamination, there is a method of making the liquid detergent a composition having a high surfactant concentration (concentrated composition).

As a liquid detergent of a concentrated composition, for example, 50 to 70% by mass of a specific alkylene oxide adduct (nonionic surfactant) and 1 to 1 of a non-soap anionic surfactant based on the total mass of the liquid detergent. A liquid detergent containing 10% by mass and a water-miscible organic solvent has been proposed (see Patent Document 2).

Patent Document 1: Japanese Patent Publication No. 2007-500268 Patent Document 2: Japanese Unexamined Patent Publication No. 2009-173858

However, there is a problem in that the liquid detergent having a concentrated composition as described in Patent Document 2 easily penetrates into clothing, so that the liquid detergent is difficult to stay on the cloth, and sufficient coating cleaning power cannot be exhibited.

For example, if the viscosity of the liquid detergent is increased, the liquid detergent tends to stay on the cloth. However, liquid detergents with high viscosity have poor fluidity, are difficult to pour into the cap, and have problems in usability, such as poor discharging property from the cap to the inlet port of the washing machine and poor discharging property from the inlet port.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent that is excellent in coating cleaning power and also excellent in usability.

As a result of intensive study, the inventors of the present invention selected at least one component selected from the group consisting of a specific nonionic surfactant, a specific triglyceride component, and a higher alcohol (for example, an alcohol having 6 to 18 carbon atoms), and an anionic surfactant. It has been found that the above-described problem is solved by a liquid detergent in which a surfactant is used in combination, and a surfactant is added at a high concentration.

That is, the present invention has the following aspects.

[1] The following (A) component, (B) component, and (C) component are contained, and the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent, The liquid cleaner:

(A) component: selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) Nonionic surfactant containing at least one compound;

(B) component: at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and an alcohol having 6 to 18 carbon atoms; And (C) component: Anionic surfactant;

[Formula 1]

In formula (a-1), R ¹ is a C 9 to C 13 hydrocarbon group, R ² is a C ² to C 4 alkylene group, R ³ is a C 1 to C 4 alkyl group, m is an average repeat of OR ² It is a number from 5 to 25 representing a number. ;

[Formula 2]

In formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, s is a number of 5 to 20 representing the average repeat number of EO, t is a number of 1 to 4 representing the average repetition number of PO; [-(EO) _s -(PO) _t -] means that EO and PO may be mixed and arranged regardless of the order of -(EO) _s -(PO) _t -. ;

[Formula 3]

In formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p represents the average repetition number of A ¹ O, q represents the average repetition number of A ² O, p>0, q>0, and p+q is a number of 10 or more and less than 60;

[Formula 4]

In formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group, a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19. .

[2] The liquid detergent according to [1], wherein the (C) component/(A) component which is a mass ratio of the component (C) and the component (A) is 0.02 to 0.7.

The liquid detergent of the present invention is excellent in coating cleaning power and also excellent in usability.

Hereinafter, the present invention will be described in detail.

The liquid detergent of the present invention contains the following (A) component, (B) component, and (C) component.

<(A) component>

(A) component is a nonionic surfactant containing at least one compound selected from the group consisting of the following compound (A1), the following compound (A2), and the following compound (A4). (A) component is a component which imparts cleaning performance to the liquid detergent of the present invention. Component (A) is in addition to at least one compound selected from the group consisting of compound (A1), compound (A2) and compound (A4), and nonionic surfactants other than those (hereinafter referred to as ``other nonionic surfactants It may also contain ".").

(Compound (A1))

Compound (A1) is a compound represented by the following general formula (a-1).

[Formula 5]

(In formula (a-1), R ¹ is a C 9 to C 13 hydrocarbon group, R ² is a C ² to C 4 alkylene group, R ³ is a C 1 to C 4 alkyl group, m is the average of OR ² It is a number from 5 to 25 indicating the number of repetitions.)

In the formula (a-1), R ¹ is a hydrocarbon group having 9 to 13 carbon atoms. The hydrocarbon group may be linear or branched, and may contain a cyclic structure.

As R ^{1, an} aliphatic hydrocarbon group is preferable, and a linear or branched alkyl group, or a linear or branched alkenyl group is more preferable. The number of carbon atoms in the hydrocarbon group is 9 to 13, preferably 10 to 13, and more preferably 11 to 13. When the number of carbon atoms is 9 or more, the cleaning power increases. On the other hand, when carbon number is 13 or less, liquid stability improves, and gelation in particular is suppressed.

R ² is an alkylene group having 2 to 4 carbon atoms, and an ethylene group or a propylene group is preferable. In addition, the ethylene group referred to herein refers to a structure represented by the structure of -CH ₂ CH ₂ -, and the propylene group refers to a structure represented by -CH ₂ CH ₂ CH ₂ .

The m ORs ² may all be the same or different. That is, one type of alkylene group in one molecule may be sufficient, and a combination of two or more types may be used. In particular, it's good to lather when washing. In order to be inexpensive, it is preferable that all of the m ORs ² are oxyethylene groups or are mixed with oxyethylene groups and oxypropylene groups.

When the alkylene group is a combination of two or more types, it is not particularly limited as a method of adding OR ² . For example, as an addition method when an oxyethylene group and an oxypropylene group are mixed, random addition may be sufficient and block addition may be sufficient. As a method of block addition, a method of adding propylene oxide after adding ethylene oxide, a method of adding ethylene oxide after adding propylene oxide, and adding propylene oxide after adding ethylene oxide, The method of adding ethylene oxide again, etc. are mentioned.

R ³ is an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to ³ carbon atoms.

Specific examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Among them, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

When carbon number is 1 or more, precipitation at the time of low temperature storage is easy to be suppressed. On the other hand, when the number of carbon atoms is 4 or less, the solubility of the liquid detergent in water under low temperature conditions is improved.

m is a number of 5 to 25 representing the average repeating number (average added mole number) of the OR ² group (oxyalkylene group). When m is 5 or more, the cleaning power, in particular, the cleaning power against sebum contamination is improved. On the other hand, when m is 25 or less, the solubility of the liquid detergent in water is improved. When all of the m ORs ² are oxyethylene groups, 5 to 20 are preferable and, as for m, 12 to 18 are more preferable. In addition, m may be an integer or may include a decimal number.

In m ORs ² , when an oxyethylene group and an oxypropylene group are mixed, m is preferably 12 to 21. At this time, the average repetition number of the oxypropylene group is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or more and 3 or less. When the average repetition number of the oxypropylene group exceeds 5, there is a concern that the cleaning power and liquid stability (transparency uniformity, stability over time, etc.) as a liquid cleaning agent may decrease.

Here, the "average number of repetitions of the OR ² group (average number of moles added)" means the average number of moles of alkylene oxide added to 1 mole of the fatty acid ester to be used.

The "average number of moles added" in this specification can be calculated by, for example, NMR.

In the compound (A1), the naro ratio indicating the ratio of the distribution of the compound (alkylene oxide adduct) with a different OR ² repeating number is preferably 20% by mass or more with respect to the total mass of the compound (A1). It is preferable that the upper limit of the naro ratio is substantially 80% by mass or less. This naro ratio is 20 to 80 mass%, more preferably 20 to 50 mass%, and since liquid stability and solubility in water are further improved, it is still more preferably 30 to 45 mass%.

The higher this naro ratio, the easier it is to obtain good cleaning power. In addition, when the naro ratio is 20% by mass or more, particularly 30% by mass or more, it becomes easy to obtain a liquid detergent with little odor of raw materials derived from compound (A1). This is a fatty acid ester that is a raw material of the compound (A1) coexisting with the compound (A1) present in the product of the compound (A1) after preparation of the compound (A1), and m in the general formula (a-1) is 1 Or, it is because the alkylene oxide adduct represented by 2 decreases.

In the present specification, the "naro rate" refers to a value expressed by the following formula (S), which indicates the ratio of the distribution of compounds with different repetitions of OR ² .

[Equation 1]

In the above formula (S), m _max represents the number of repetitions of OR ² of the compound (alkylene oxide adduct) most often present in the entire compound (A1).

i represents the number of repetitions of OR ² .

Yi, the compound (A1) represents a proportion (% by weight) of the total weight of the compound (A1) in the present iteration number i Compounds of OR ² in which the body (alkylene oxide adduct).

The naro ratio can be controlled by, for example, a method for producing compound (A1).

The method for producing compound (A1) is not particularly limited, but for example, a method of adding an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (refer to Japanese Unexamined Patent Publication No. 2000-144179) It can be manufactured easily.

As such a suitable surface-modified composite metal oxide catalyst, specifically, it was surface-modified by a metal hydroxide or the like, metal ions (Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , Tl ^{3 +} , Co ^{3 +} , Sc ^{3 +} , La ^3+, Mn ^{+ 2,} etc.) is a complex metal oxide catalyst such as magnesium oxide is added; And a calcined product catalyst of hydrotalcite surface-modified with at least one component selected from the group consisting of metal hydroxides and metal alkoxides.

In addition, in the surface modification of the composite metal oxide catalyst, when the mixing ratio of the composite metal oxide with at least one component selected from the group consisting of metal hydroxide and metal alkoxide is 100 parts by mass of the composite metal oxide, the composite metal The ratio of at least one component selected from the group consisting of a metal hydroxide and a metal alkoxide per 100 parts by mass of the oxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

Compound (A1) may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

When the total mass of the liquid detergent is 100% by mass, the content of the compound (A1) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass. When the content of the compound (A1) is 1% by mass or more, good cleaning power can be obtained. On the other hand, when the content of the compound (A1) is 70% by mass or less, gelation with time becomes difficult to occur.

(Compound (A2))

Compound (A2) is a compound represented by the following general formula (a-2).

[Formula 6]

(In formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s is a number of 5 to 20 representing the average repeat number of EO , t is a number of 1 to 4 representing the average repetition number of PO; [-(EO) _s -(PO) _t -] is the order of the formula-(EO) _s -(PO) _t- It indicates that it may be arranged in a mixture without depending on.)

In the formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms. The hydrocarbon group may be linear or branched, and may contain a cyclic structure.

As R ^{4, an} aliphatic hydrocarbon group is preferable, and a linear or branched alkyl group, and a linear or branched alkenyl group are more preferable. The hydrocarbon group has 10 to 20 carbon atoms, preferably 12 to 18, and more preferably 12 to 14. When the number of carbon atoms is 10 or more, the cleaning power increases. On the other hand, when carbon number is 20 or less, liquid stability improves, and gelation in particular is suppressed.

Compound (A2) may be a single chain length (a mixture of chain lengths) or a mixture of a plurality of chain lengths. R ⁴ is derived from alcohol (R ⁴ -OH) as a raw material, and examples of the alcohol include palm oil, Alcohol derived from natural oils, such as palm oil or tallow; Synthetic alcohol derived from petroleum, etc. are mentioned.

s is a number of 5 to 20 representing the average repetition number (average added mole number) of an EO group (oxyethylene group). s may be an integer or may include a decimal number. When s is within the above range, the cleaning power, in particular, the cleaning power against sebum contamination is improved. s is preferably 5 to 18.

t is a number of 1 to 4 representing the average repetition number (average added mole number) of the PO group (oxypropylene group). t may be an integer or may include a decimal number. When t is within the above range, gelation of the liquid detergent is easily suppressed, and good clothability can be easily obtained at the time of rinsing. t is preferably 1 to 3.

Here, "average repetition number of EO groups (average number of moles added)" means the average of the number of moles of ethylene oxide added to 1 mole of alcohol to be used.

Here, "average repetition number of PO group (average number of moles added)" means the average number of moles of propylene oxide added to 1 mole of alcohol to be used.

In compound (A2), [-(EO) _s -(PO) _t -] means that EO and PO may be arranged in a mixture, regardless of the sedentary order. That is, EO and PO may be added in a block form or may be added in a random form. As an addition method in the case where EO and PO are added in a block form, the addition method previously exemplified in the description of compound (A1) can be mentioned. In particular, since the rinsing property in washing in a fully automatic washing machine becomes better, a method of adding propylene oxide after adding ethylene oxide and then adding ethylene oxide again is preferable.

In the compound (A2), the distribution of the added mole number of EO and PO is not particularly limited, and the distribution of the added mole number can be controlled by a method for preparing compound (A2) or the like.

For example, when EO and PO are added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, there is a tendency to have a relatively wide addition mole number distribution. In addition, oxidation by adding metal ions such as Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , Tl ^{3 +} , Co ³⁺ , Sc ^{3 +} , La ^{3 +} and Mn ^{2 +} as described in Japanese Patent Publication No. 6-15038 When EO and PO are added to a hydrophobic raw material using a specific alkoxylation catalyst such as magnesium, there is a tendency to have a relatively narrow addition mole number distribution.

Compound (A2) may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

When the total mass of the liquid detergent is 100% by mass, the content of the compound (A2) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass. When the content of the compound (A2) is 1% by mass or more, good cleaning power can be obtained. On the other hand, when the content of the compound (A2) is 70% by mass or less, gelation with time becomes difficult to occur.

(Compound (A4))

Compound (A4) is a compound represented by the following general formula (a-4).

[Formula 7]

(In the formula, R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p represents the average repeat number of A ¹ O, and q Represents the average number of repetitions of A ² O, p>0, q>0, and p+q is a number of 10 or more and less than 60.)

In the formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms. From the viewpoint of cleaning properties, an alkyl group having 10 to 18 carbon atoms or an alkenyl group having 10 to 18 carbon atoms is preferable, and may be linear or branched.

When the number of carbon atoms of R ¹ is 10 or more, the effect of preventing recontamination is increased, and the cleaning power is improved. On the other hand, when the number of carbon atoms of R ¹ is 20 or less, solubility in water is improved.

In the formula (a-4), A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms, and an oxyethylene group and an oxypropylene group are preferable. A ¹ O and A ² O may be the same or different.

In the above formula (a-4), p represents the average number of repetitions of A ¹ O, q represents the average number of repetitions of A ² O, and p and q are each independently greater than 0. p+q is a number of 10 or more and less than 60. When p+q is less than 10, it becomes difficult to obtain a cleaning effect. On the other hand, when p+q is 60 or more, as the molecular weight of compound (A4) itself increases, the number of moles of compound (A4) in the composition decreases at the same amount, so that the cleaning effect tends to decrease. Among these, p+q is preferably 15 or more and 40 or less, and more preferably 15 or more and 35 or less, since the cleaning power and recontamination prevention effect are more enhanced.

(A ¹ O) _p may be a repeating structure of only an oxyethylene group, a repeating structure of only an oxypropylene group, a repeating structure of only an oxybutylene group, oxyethylene group, oxypropylene group, and oxybutylene group are mixed It may be a structure that is present. Among them, a repeating structure of only an oxyethylene group, a structure in which an oxyethylene group and an oxypropylene group are mixed are preferable, and a repeating structure of only an oxyethylene group is more preferable.

In the case of a structure in which an oxyethylene group and an oxypropylene group are mixed, the oxyethylene group and the oxypropylene group may be repeated in a random form or may be repeated in a block form. In this case, it is preferable that the total amount of oxyethylene groups in compound (A4) is 60% by mass or more with respect to the total mass of all oxyalkylene groups in compound (A4) from the viewpoint of solubility in water.

(A ² O) _q has the same meaning as the above (A ¹ O) _p, and a preferred example is also the same.

As the compound (A4), polyoxyethylene (20) hexadecylamine (R ¹ = alkyl group having 16 carbon atoms, average repetition number of oxyethylene group 20, p+q = 20, polyoxyethylene (15) uzialkylamine (R ¹ = an average repetition number of an alkyl group having 14 to 18 carbon atoms, an oxyethylene group having an average repetition number of 15, p+q = 15, polyoxyethylene (50) octadecylamine (R ¹ = an average repetition number of an alkyl group having 18 carbon atoms and an oxyethylene group 50 , p+q=50, polyoxyethylene (42) polyoxypropylene (12) hexadecylamine (R ¹ = alkyl group having 16 carbon atoms, average repetition number of oxyethylene group 42, average repetition number of oxypropylene group 12, p +q=54), polyoxyethylene (28) polyoxypropylene (8) alkylamine (R ¹ = alkyl group having 12 to 14 carbon atoms, average repetition number of oxyethylene group 28, average repetition number of oxypropylene group 8 , equivalent to p+q=36), etc. are appropriate.

Compound (A4) may be used alone or in combination of two or more.

When the total mass of the liquid detergent is 100% by mass, the content of the compound (A4) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass. When the content of the compound (A4) is 1% by mass or more, the effect of preventing recontamination is enhanced, and good cleaning power can be obtained. On the other hand, when the content of the compound (A4) is 70% by mass or less, it is preferable in that the fluidity of the liquid detergent becomes good, and it is excellent in handling properties at the time of manufacture.

(Other nonionic surfactants)

(Compound (A3))

Compound (A3) is a compound represented by the following general formula (a-3).

[Formula 8]

(In formula (a-3), R ⁵ is a hydrocarbon group having 10 to 22 carbon atoms, EO is an oxyethylene group, and n is a number of 5 to 20 representing the average repeat number of EO.)

In the formula (a-3), R ⁵ is a hydrocarbon group having 10 to 22 carbon atoms. The hydrocarbon group may be linear or branched, and may contain a cyclic structure. Further, the hydrocarbon group may have an unsaturated bond or may be a mixture of a single chain length and a plurality of chain lengths.

As R ^{5, an} aliphatic hydrocarbon group is preferable, and a linear or branched alkyl group or a linear or branched alkenyl group is more preferable. The number of carbon atoms in the hydrocarbon group is 10 to 22, preferably 10 to 20, and more preferably 10 to 18. When the number of carbon atoms is 10 or more, the cleaning power is further improved. On the other hand, when the number of carbon atoms is 22 or less, liquid stability is further improved, and gelation in particular is more suppressed.

R ⁵ is derived from alcohol (R ⁵ -OH) as a raw material, and examples of the alcohol include alcohols derived from natural oils such as palm oil, palm oil, or tallow, synthetic alcohols derived from petroleum, and the like.

n is a number of 12 to 20 representing the average repetition number (average added mole number) of EO (oxyethylene group), and 12 to 18 are preferable, and 12 to 16 are more preferable. n may be an integer or may include a decimal number. When n is 12 or more, it becomes easy to obtain a liquid detergent with little smell of raw materials derived from compound (A3). On the other hand, when n is 20 or less, it is possible to suppress the HLB from becoming too high, and the cleaning power against sebum contamination can be maintained satisfactorily. In particular, when n is 12 to 16, it exhibits high cleaning power against sebum contamination.

In the compound (A3), the distribution of the added mole number of EO is not particularly limited, and the distribution of the added mole number can be controlled by a method for preparing compound (A3) or the like.

For example, when EO is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, there is a tendency to have a relatively wide addition mole number distribution. In addition, oxidation by adding metal ions such as Al ^{3 +} , Ga ^{3 +} , In ^{3 +} , Tl ^{3 +} , Co ^{3 +} , Sc ³⁺ , La ^{3 +} and Mn ^{2 +} described in Japanese Patent Publication No. 6-15038 When EO is added to a hydrophobic raw material using a specific alkoxylation catalyst such as magnesium, there is a tendency to have a relatively narrow addition mole number distribution.

As a specific example of the compound (A3), Shell agent: a brand name Neodol (C12/C13), Sasol product: A compound obtained by adding 12 and 15 moles of EO to an alcohol such as Safol23 (C12/C13); The P&G company make: of a compound obtained by adding 9, 12 and 15 moles of EO to natural alcohols such as brand names CO-1214 and CO-1270; Compounds obtained by adding 9, 12, and 15 moles of EO to a secondary alcohol having 12 to 14 carbon atoms (the Nippon Catalyst Co., Ltd. product, Sofutanol 0, 120 and 150), and the like.

Compound (A3) may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

In addition, examples of other nonionic surfactants that may be included in addition to compound (A3) include alkyl polyglucoside (APG), fatty acid diester (manufactured by Lion Corporation: brand name Lionone DT-600S), and alkylamine oxide (manufactured by Lion Corporation. : Aromox DMC-W), etc. are mentioned.

The content of the other nonionic surfactant is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. . When the content of the other nonionic surfactant is 1% by mass or more, better cleaning power can be obtained. On the other hand, when the content of the other nonionic surfactant is 70% by mass or less, gelation with time becomes more difficult to occur.

As (A) component, compound (A1) is preferable. Compound (A1) is more easily blended with other components than compound (A2) and compound (A4), and is more easily concentrated. In the case of compound (A1), since a solvent is not required when concentrating, the fragrance is hardly damaged.

Moreover, in order to reduce the viscosity of a liquid detergent and improve usability, it is preferable to use compound (A3) together. Compared to the case of using only at least one compound selected from the group consisting of compound (A1), compound (A2), and compound (A4), when compound (A3) is used in combination with the above compound, compound (A1) and compound (A2) ), and at least one compound selected from the group consisting of compound (A4) and a molecular aggregate consisting of compound (A3), the packing property between molecules is weakened, and the viscosity of the liquid detergent is thought to decrease. . In particular, it is preferable to use compound (A1) and compound (A3) in combination.

In addition, the "molecular aggregate" herein refers to at least one compound selected from the group consisting of compound (A1), compound (A2), and compound (A4), and compound (A3) under conditions such as temperature and pressure of the solution. Means an aggregate collected by

The sum of the compound (A1) and the compound (A2) and the mass ratio of the compound (A3) (the sum of the compound (A1) and the compound (A2)/compound (A3))) is preferably 0.02 to 4.5, and 1.25 to 4 It is more preferable, and 2-4 are still more preferable. When the mass ratio is 0.02 or more, gelation with time becomes more difficult to occur. On the other hand, when the mass ratio is 4.5 or less, the viscosity tends to decrease and the usability tends to improve.

<(B) component>

Component (B) is at least one compound selected from the group consisting of the following compound (B1) and higher alcohol (B2).

(Compound (B1))

Compound (B1) is a compound (triglyceride component) represented by the following general formula (b-1).

[Formula 9]

(In formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group, a+b=7 to 19, c+d=7 to 19, and e+f=7 to 19.)

In the formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group. Z ^{1 to} Z ³ may be the same or different.

Further, a+b=7-19, c+d=7-19, and e+f=7-19, preferably a+b=11-15, c+d=11-15, and e+ f=11-15, more preferably a+b=13-15, c+d=13-15, and be+f=13-15. When a+b, c+d, and e+f are each 7 or more, the volume of the hydrophobic group swells, and coating cleaning power is increased. On the other hand, when a+b, c+d, and e+f are respectively 19 or less, the risk of solidification due to the swelling of the volume of the hydrophobic group is reduced.

Compound (B1) Examples of, Z ¹ ~Z ³ is a hydroxy group in compound (B1-1), Z ¹ ~Z ³ a and the like can be given the compound (B1-2) a hydrogen atom. As compound (B1-1), hydrogenated castor oil is particularly preferable, and as compound (B1-2), hydrogenated palm oil is particularly preferable.

In addition, as the compound (B1), it may be produced by a known method, or a commercial item may be used. For example, as the compound (B1-1), "Castar Wax A Flakes" manufactured by Nichiyu Corporation, and as the compound (B1-2), "Palm extremely hardened oil A" manufactured by Shinnihon Ewha Corporation, etc. are mentioned.

Compound (B1) may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

When the total mass of the liquid detergent is 100% by mass, the content of the compound (B1-1) is preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass, and still more preferably 0.3 to 1% by mass. Do. When the content of the compound (B1-1) is 0.1% by mass or more, good cleaning power can be expressed. On the other hand, when the content of the compound (B1-1) is 5% by mass or less, the risk of causing solidification is reduced.

The content of the compound (B1-2) is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and still more preferably 2 to 4% by mass when the total mass of the liquid detergent is 100% by mass. Do. When the content of the compound (B1-2) is 0.5% by mass or more, good cleaning power can be expressed. On the other hand, when the content of the compound (B1-2) is 10% by mass or less, the risk of causing solidification is reduced.

(Advanced Alcohol (B2))

The higher alcohol (B2) is a monohydric alcohol having 6 or more and 18 or less carbon atoms.

The more the volume of the hydrophobic part is swollen, the easier it is to form a structural liquid. Therefore, as the higher alcohol (B2), an alcohol having 12 or more carbon atoms is preferable, and a branched alcohol is particularly preferable. The number of carbon atoms is preferably 18 or less. When the carbon number of the higher alcohol (B2) is 18 or less, a liquid detergent containing the higher alcohol (B2) can form a structural liquid without causing solidification.

Here, the "structural liquid" means a liquid having thixotropic properties. In addition, ``thixotropy'' is a property exhibited by an intermediate substance between a calcined solid such as a gel and a non-Newtonian liquid such as a sol. Specifically, the viscosity gradually decreases when subjected to shear stress and becomes a liquid state. It is a property that the viscosity increases gradually and finally becomes solid.

In the present invention, when the component (A) is included and the component (B) is not included, the liquid detergent is in the form of a spherical micelle, but when the component (B) is incorporated into such a liquid detergent, The critical filling parameter (CPP), which correlates the molecular structure of the surfactant and the self-organizing structure, approaches 1, and changes to a liquid having thixotropic properties.

Examples of the higher alcohol (B2) include "ISOFOL12" manufactured by SASOL.

Higher alcohol (B2) may be used alone or in combination of two or more.

The content of the higher alcohol (B2) is preferably 1 to 7% by mass, more preferably 2 to 6% by mass, and still more preferably 3 to 5% by mass when the total mass of the liquid detergent is 100% by mass. . When the content of the higher alcohol (B2) is 1% by mass or more, good cleaning power can be expressed. On the other hand, when the content of the higher alcohol (B2) is 7 mass% or less, it becomes easier to form a structural liquid without causing solidification.

<(C) component>

(C) A component is an anionic surfactant.

The anionic surfactant is not particularly limited, and a known anionic surfactant can be used. Specifically, straight-chain alkylbenzenesulfonic acid or a salt thereof; α-olefin sulfonate; A linear or branched alkyl sulfuric acid ester salt; Alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt; Alkanesulfonic acid salts having an alkyl group; α-sulfo fatty acid ester salts, and the like.

Examples of these salts include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; Alkanolamine salts, such as monoethanolamine and diethanolamine, etc. are mentioned.

In addition to the above-described component (C), for example, higher fatty acid salts having 10 to 20 carbon atoms, alkyl ether carboxylic acid salts, polyoxyalkylene ether carboxylic acid salts, alkyl (or alkenyl) amide ether carboxylic acid salts And carboxylic acid type anionic surfactants such as acylaminocarboxylic acid salts; Phosphoric acid ester-type anionic surfactants such as alkyl phosphate salts, polyoxyalkylene alkyl phosphate salts, polyoxyalkylene alkyl phenyl phosphate ester salts, and glycerin fatty acid ester monophosphate salts.

Examples of these salts include alkali metal salts such as sodium and potassium; Alkaline earth metal salts such as magnesium; Alkanolamine salts, such as monoethanolamine and diethanolamine, etc. are mentioned.

Among the above, as the linear alkylbenzenesulfonic acid or a salt thereof, a linear alkylbenzenesulfonic acid having 8 to 16 carbon atoms or a salt thereof of the linear alkyl group is preferable, and a linear alkylbenzenesulfonic acid having 10 to 14 carbon atoms or a salt thereof is particularly preferable.

As the α-olefin sulfonate, an α-olefin sulfonate having 10 to 20 carbon atoms is preferable.

As the alkyl sulfuric acid ester salt, an alkyl sulfuric acid ester salt having 10 to 20 carbon atoms is preferable.

The alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt has a linear or branched alkyl group having 10 to 20 carbon atoms, or a linear or branched alkenyl group having 10 to 20 carbon atoms, and has an average repeat number of 1 to 10 Alkyl ether sulfuric acid ester salt or alkenyl ether sulfuric acid ester salt (that is, polyoxyethylene alkyl ether sulfuric acid ester salt or polyoxyethylene alkenyl ether sulfuric acid ester salt) to which moles of ethylene oxide are added is preferable. In addition, an average of 0.5 to 10 moles of alkylene oxides having 2 to 4 carbon atoms or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) is added. Alkyl (or alkenyl) ether sulfuric acid ester salts having a linear or branched alkyl group (or alkenyl group) having 10 to 20 carbon atoms (hereinafter, sometimes referred to as AES or AEPS) are preferred.

Examples of the alkanesulfonic acid salt include alkanesulfonic acid salts having 10 to 20 carbon atoms, preferably alkanesulfonic acid salts having 14 to 17 carbon atoms, and particularly preferably secondary alkanesulfonic acid salts.

As the α-sulfo fatty acid ester salt, an α-sulfo fatty acid ester salt having 10 to 20 carbon atoms is preferable.

These anionic surfactants are readily available on the market. Further, it may be synthesized by a known method.

(C) As a component, among the above, linear alkylbenzenesulfonic acid or its salt; Alkanesulfonic acid salts; Polyoxyethylene alkyl ether sulfuric acid ester salt; The number of carbon atoms obtained by adding an average of 0.5 to 10 moles of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) of an alkylene oxide having 2 to 4 carbon atoms Alkyl (or alkenyl) ether sulfuric acid ester salts having 10 to 20 linear or branched alkyl groups (or alkenyl groups); α-olefin sulfonates and higher fatty acid salts; At least one anionic surfactant selected from the group consisting of and the like is preferred.

<optional ingredient>

In the liquid detergent of the present invention, in addition to the above (A) component, (B) component, and (C) component, if necessary, components commonly used in liquid detergents can be blended within a range that does not impair the effects of the present invention. have. For example, the components shown below are mentioned.

(Optional surfactant)

The liquid detergent of the present invention may contain a surfactant (hereinafter, it may be referred to as an arbitrary surfactant) excluding the component (A) and the component (C).

As an arbitrary surfactant, a cationic surfactant, etc. are mentioned.

Examples of the cationic surfactant include dimethylaminopropylamide caprylate, dimethylaminopropylamide caprylate, dimethylaminopropylamide laurate, dimethylaminopropylamide myristic acid, dimethylaminopropylamide palmitate, and dimethylamino stearate. Long-chain aliphatic amide alkyl tertiary amines such as propylamide, dimethylaminopropylamide behenate and dimethylaminopropylamide oleate, or a salt thereof; Aliphatic ester alkyl tertiary amines such as palmitate ester propyl dimethyl amine and stearate ester propyl dimethyl amine, or salts thereof; Diethanol aminopropyl amide palmitate, diethanol amino propyl amide stearic acid, and the like. These cation surfactants may be used alone or in combination of two or more as appropriate.

Among them, caprylic acid dimethylaminopropylamide, caprylic acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid Particularly preferred are dimethylaminopropylamide, oleic acid dimethylaminopropylamide or a salt thereof. Mixtures thereof are also preferred.

In addition, as a cationic surfactant, it can be suitably selected and used among well-known cationic surfactants. For example, cationic surfactants such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl benzyl dimethyl ammonium salt, and alkyl pyridinium salt can also be used.

(Water)

It is preferable that the liquid detergent of this invention contains water.

When the total mass of the liquid detergent is 100% by mass, the content of water is preferably 5 to 35% by mass, and more preferably 20 to 35% by mass. When the water content is 5% by mass or more, the liquid detergent is difficult to gel, and fluidity and stability can be maintained satisfactorily. On the other hand, when the water content is 35% by mass or less, the (A) component and (B) component can be contained in the liquid detergent in an optimal range, and the structural liquid is easily formed.

(solvent)

The liquid detergent of the present invention may contain a solvent. As the solvent, a solvent conventionally blended with a medical detergent or the like can be used.

Examples of the solvent include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; Glycols such as propylene glycol, butylene glycol, and hexylene glycol; Polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, polyethylene glycol having an average molecular weight of about 1000, and dipropylene glycol; Alkyl ethers, such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether, etc. are mentioned.

The sum of the content of water and solvent is preferably 15 to 45% by mass, and more preferably 25 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. When the total content of water and solvent is 15% by mass or more, the liquid detergent is difficult to gel, and fluidity and stability can be maintained satisfactorily. On the other hand, when the total content of the water and the solvent is 45% by mass or less, the (A) component and the (B) component can be contained in the liquid detergent within the optimum range, and the structural liquid is easily formed.

(Inorganic salt)

The liquid detergent of the present invention may contain an inorganic salt, particularly preferably in combination with the component (C). In the inorganic salt, since the hydrophilic group of the component (C) can cancel the charge of the same charge, it becomes easier to form a structural liquid.

As an inorganic salt, sodium chloride, potassium chloride, sodium citrate, potassium nitrate, potassium sulfate, etc. are mentioned, for example.

Inorganic salts may be used singly or in combination of two or more as appropriate.

The content of the inorganic salt is preferably 0.2 to 1% by mass when the total mass of the liquid detergent is 100% by mass. When the content of the inorganic salt is 0.2% by mass or more, the cleaning power is improved. On the other hand, when the content of the inorganic salt is 1% by mass or less, it is possible to suppress a decrease in cleaning power due to an excess salt.

(Water-soluble particles, water-insoluble particles)

The liquid detergent of the present invention may contain particles (ie, water-soluble particles and water-insoluble particles) that are difficult to dissolve in the components constituting the liquid detergent.

As such particles, specifically, a capsule perfume or a cloth containing an active ingredient instead of it, beads and pearlescent agents for imparting unique product aesthetics, bentonite, carboxymethylcellulose (CMC), and Laponite S482 And cluster dextrin.

As a capsule perfume, BLUEFLOWERPOP "FFMHN2814" manufactured by Filmenich Corporation; AURORACAPS and COSMICCAPS manufactured by Jibodan Co. UNICAP101 and UNICAP503 manufactured by IFF, etc. are mentioned.

The liquid detergent of the present invention may contain clusterdextrin, and by containing clusterdextrin, reverberation properties can be further improved. As a specific example of cluster dextrin (highly branched cyclic dextrin), "Cluster dextrin" (registered trademark) of Glyco Nutrition Foods Co., Ltd. is mentioned. These particles may be used singly or in combination of two or more as appropriate.

The content of at least one component selected from the group consisting of water-soluble particles and water-insoluble particles is preferably 0.05 to 5% by mass when the total mass of the liquid detergent is 100% by mass.

(Urea or derivative thereof)

The liquid detergent of the present invention may contain urea or a derivative thereof, and is particularly preferably used in combination with compound (A1). Examples of urea or its derivatives include urea [CO(NH ₂ ) ₂ ], urea double salts, and derivatives of urea other than these.

As the urea double salt, HNO ₃ ·CO(NH ₂ ) ² , H ₃ PO ₄ ·CO(NH ₂ ) ₂ , H ₂ C ₂ O ₄ ·2CO(NH ₂ )2, Ca(NO ₃ ) ₂ ·4CO(NH ₂ ) ₂ , CaSO ₄ ·4CO(NH ₂ ) ₂ , Mg(NO ₃ ) ₂ ·CO(NH ₂ ) ₂ ·2H ₂ O, CaSO ₄ ·(5∼6)4CO(NH ₂ ) ₂ ·2H ₂ O Etc. can be used.

In the present invention, the "derivative of urea" includes a compound having a partial structure represented by the following general formula (d-1). Among the derivatives of urea, compounds represented by the general formula (d-2) are mentioned as suitable compounds.

[Formula 10]

(In the formula (d-2), R ^a is a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 2 carbon atoms; R ^b , R ^c and R ^d are each independently a hydrogen atom, a methyl group, or an ethyl group. to be.)

Examples of the compound represented by the above formula (d-2) include 1,3-dimethylurea and N-(2-hydroxyethyl)urea.

Urea may be used alone or in combination of two or more.

The content of urea in the liquid detergent is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the liquid detergent. When the content exceeds the upper limit, ammonia tends to be generated as a decomposition product after storage, and there is a problem of odor as a liquid detergent product.

(silicon)

The liquid detergent of the present invention may contain silicone. By containing silicone, it is possible to further improve rinse performance and foam suppression during manufacture.

Examples of the silicone include polyether-modified silicone and amino-modified silicone, and among them, polyether-modified silicone is preferred.

The polyether-modified silicone is not particularly limited as long as it has a polyether group such as polyethylene oxide or polypropylene oxide as a functional group. Further, if a polyether group such as polyethylene oxide or polypropylene oxide is introduced, another functional group may be introduced.

Commercially available polyether-modified silicones include SH3772M, SH3775M, SH3749, SF8410, SH8700, BY22-008, SF8421, SILWET L-7001, SILWET L-7002, SILWET L-7602, SILWET L manufactured by Toray Dow Corning. -7604, SILWET FZ-2104, SILWET FZ-2164, SILWET FZ-2171, ABN SILWET FZ-F1-009, ABN SILWET FZ-F1-009-05, ABN SILWET FZ-F1-009-09, ABN SILWET FZ- F1-009-54, ABN SILWET FZ-2222 (above, brand name); Shin-Etsu Chemical Co., Ltd. KF352A, KF6008, KF615A, KF6016, KF6017 (above, brand name); GE Toshiba Silicon Corporation's TSF4450 and TSF4452 (above, brand name), etc. are mentioned.

Further, examples of the silicone antifoaming agent include KM-7750, KM-90, KM-98, KS-538, KS-66, KS-69 (above, brand name) manufactured by Shin-Etsu Chemical Industries, Ltd. and the like.

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

(Other optional ingredients)

The liquid detergent of the present invention may contain other optional components acceptable as a liquid detergent.

Other optional components that can be accepted as liquid detergents include dispersion media, hydrotropes, detergent builders, stabilizers (e.g., sodium benzoate, citric acid, sodium citrate, polyhydric alcohol, polyethylene glycol, known in the field of liquid detergents). Alkyl ether, polypropylene glycol alkyl ether, etc.), alkali agents (for example, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, etc.), metal ion scavenger (for example, malonic acid, succinic acid, malic acid) , Diglycolic acid, tartaric acid, citric acid, or salts thereof), silicone, etc., texture improving agents, preservatives, fluorescent agents, migration inhibitors, pearl agents, antioxidants (e.g., dibutylhydroxytoluene, distyrenated cresol, sodium sulfite) , Sodium hydrogen sulfite, etc.), enzymes, and additives such as pigments, flavoring agents and emulsifying agents, and a pH adjuster as general purpose coloring agents and coloring agents.

In addition, the liquid detergent of the present invention may contain enzymes conventionally blended with medical detergents and the like. By containing an enzyme, coating cleaning power is further improved.

In addition, in the present invention, "enzyme" represents an enzyme preparation.

Examples of the enzyme include protease, amylase, lipase, cellulase, mannase, and cellulase.

As the protease, like serine protease, a protease having serine, histidine, and aspartic acid in the molecule is preferable.

As a specific example of a protease, trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase Ultra 2.5L, Liquanase 2.5 available as protease preparations from Novozyme Injection. L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L; Trade names Purafect L, Purafect OX, Properase L and the like available from Genencore Co., Ltd. are mentioned.

Specific examples of amylase include trade names Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainyme 12L, and Stainzyme Plus 12L available from Novozyme Injection as an amylase preparation; Trade name Maxamyl available from Genencore Corporation; The brand name Pruranase Amano available from Amano Enzyme Co., Ltd.; The brand name DB-250 etc. which can be obtained from Seikagaku Industrial Co., Ltd. are mentioned.

As a specific example of a lipase, brand names Lipex 100L, Lipolase 100L etc. which can be obtained from Novozyme Injection as a lipase preparation are mentioned.

As a specific example of cellulase, Keazyme 4500L (trade name, Novozyme injection, reducing sugar production amount: 253.2μM), Keazyme Puremyam 4500L (trade name, Novozyme injection, reducing sugar production amount: 307.0μM), Endorase 5000L (trade name , Novozyme injection, reducing sugar production amount: 187.0 μM), Cell Clean 4500T (brand name, novozyme injection, reducing sugar production amount: 120.6 μM), and the like endoglucanase preparations.

Among these, Keazyme 4500L and Keaenzyme Puremium 4500L are preferable, and Keazyim Puremium 4500L is more preferable.

As a specific example of a mannase, the brand name Mannaway 4L etc. which can be obtained from Novozyme Injection as a mannase preparation are mentioned.

These enzymes may be used individually by 1 type, and may be used in combination of 2 or more types suitably.

The content of the enzyme is preferably 0.1 to 3% by mass with respect to 100% by mass of the liquid detergent.

As another aspect of other optional ingredients that may be acceptable as liquid detergents, from the group consisting of stabilizers, cation surfactants, pH adjusters, silicones, perfumes, water, alkali agents, enzymes, urea, clusterdextrins, and dispersion media. It is preferred that it is at least one component selected.

As another aspect of any other optional ingredients that may be acceptable as a liquid detergent,

Sodium benzoate, citric acid, stearic acid dimethylaminopropylamide, alkyltrimethylammonium salt, sodium hydroxide, silicone, perfume, water, ethanolamine, corona agent, urea, clusterdextrin, paratoluenesulfonic acid, polyethylene glycol, ethanol, butylcarbitol (butyldi Glycol), propylene glycol, and sodium cumenesulfonate is preferably at least one component selected from the group consisting of.

<Content of each component>

(Content of all surfactants)

The content of all surfactants (hereinafter, also referred to as "all surfactants") contained in the liquid detergent is 45% by mass or more when the total mass of the liquid detergent is 100% by mass. When the content of the total surfactant is 45% by mass or more, it is possible to impart high cleaning performance to the liquid detergent and to retain the structural liquid. The content of the total surfactant is preferably 51% by mass or more, more preferably more than 51% by mass, and particularly preferably 54% by mass or more. Moreover, 80 mass% or less is preferable, 70 mass% or less is more preferable, and 60 mass% or less is still more preferable. When the content of the total surfactant exceeds 80% by mass, the liquid detergent tends to gel, and the stability may decrease.

That is, the content of all surfactants is 45% by mass or more and 80% by mass or less, preferably 51% by mass or more and 80% by mass or less, and more than 51% by mass and 70% by mass or less based on 100% by mass of the liquid detergent. Is more preferable, and 54 mass% or more and 60 mass% or less are still more preferable.

In addition, all surfactants mentioned here mean the content which combined all the surfactants contained as (A) component, (C) component, and an optional component.

(Content of (A) component)

The content of the component (A) is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 15 to 45% by mass, when the total mass of the liquid detergent is 100% by mass. When the content of the component (A) is 1% by mass or more, good cleaning power can be obtained. On the other hand, when the content of the component (A) is 70% by mass or less, gelation with time becomes difficult to occur.

(Content of (B) component)

The content of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 4% by mass, when the total mass of the liquid detergent is 100% by mass. When the content of the component (B) is 0.1% by mass or more, good cleaning power can be expressed. On the other hand, if the content of the component (B) is 10% by mass or less, the risk of causing solidification is reduced.

(Content of (C) component)

The content of the component (C) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass, and still more preferably 5 to 16% by mass, when the total mass of the liquid detergent is 100% by mass. When the content of the component (C) is 1% by mass or more, cleaning performance, particularly coating cleaning power, is improved. On the other hand, when the content of the component (C) is 20 mass% or less, liquid stability improves.

((A) component / (B) component)

As for the mass ratio ((A) component/(B) component) of (A) component and (B) component, 15-150 are preferable, 37.5-110 are more preferable, and 60-100 are still more preferable. If the proportion of the component (B) is too high, gelation occurs, and thus the fluidity and stability of the liquid detergent may decrease. On the other hand, if the proportion of the component (B) is too low, it is difficult to obtain good coating and cleaning power.

((C) component / (A) component)

The mass ratio ((C) component/(A) component) of the component (C) and the component (A) is preferably 0.02 to 0.7, more preferably 0.06 to 0.5, and still more preferably 0.1 to 0.3. If the proportion of the component (C) is too high, the cleaning power may decrease. On the other hand, if the ratio of the component (C) is too low, protein detergency and recontamination deteriorate.

<physical properties>

(Viscosity)

The liquid detergent of the present invention preferably has a viscosity of 50 to 1000 MPa·s at 60 rpm using a B-type viscometer (manufactured by TOKIMEC, rotor No. 2 or 3) at 25°C, and is 75 to 800 MPa·s. It is more preferable and it is more preferable that it is 100-500 MPa·s.

Moreover, it is preferable that the viscosity at 6 rpm by a B-type viscometer (manufactured by TOKIMEC, rotor No. 2 or 3) at 25°C is 500 to 5000 MPa·s, more preferably 500 to 3000 MPa·s, It is more preferably 500 to 2000 MPa·s.

Further, it is preferable that the TI value (viscosity at 6 rpm/viscosity at 60 rpm) expressed as a ratio of the viscosity at 6 rpm and the viscosity at 60 rpm is 2 or more. The TI value is an index indicating thixotropy, and the larger the TI value, the higher the thixotropy and means that the viscosity difference due to the change in the shear rate is large. That is, the larger the TI value, the higher the viscosity at a low shear force and a lower viscosity at a high shear force.

In the present specification, the viscosity is defined as a value at 25° C. unless there is a clue. That is, even if a value outside the range specified in the present specification is corrected to a value at 25° C., if the viscosity is within the range specified in the present specification, they are included in the scope of the present invention.

(pH)

The liquid detergent of the present invention preferably has a pH of 6 to 9, and more preferably 7 to 8 at 25°C. Since the pH is 6 to 9, in particular, even when the liquid detergent is stored for a long period, stability over time can be maintained satisfactorily.

The pH of the liquid detergent (heating at 25°C) indicates a value measured by a pH meter (manufactured by Doudeke Corporation, "HM-30G") or the like.

In the present specification, pH is defined as a value at 25°C unless there is a clue. That is, even if a pH value outside the range specified in the present specification is corrected to a pH value at 25°C, if the pH value is within the range specified in the present specification, they are included in the scope of the present invention.

The pH of the liquid detergent of the present invention can be adjusted by a pH adjuster. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; Organic acids such as polyvalent carboxylic acids and hydroxycarboxylic acids; Sodium hydroxide, potassium hydroxide, alkanolamine, ammonia, etc. are mentioned. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable, and sulfuric acid and sodium hydroxide are preferable from the viewpoint of stability over time of the liquid detergent.

The pH adjusting agent may be used individually by 1 type, and may use 2 or more types together. For example, when controlling by adding a certain amount of sulfuric acid, sodium hydroxide or the like, an inorganic acid (preferably hydrochloric acid, sulfuric acid) or potassium hydroxide can be further added for fine adjustment of the pH.

<Production method>

The manufacturing method of the liquid detergent of the present invention can be manufactured based on a routine method. For example, after dispersing the component (A), component (C), and optional components as necessary in a part of water, the solution in which the component is dispersed is heated to the melting point of component (B), and the warming To the solution, the component (B) heated to the melting point is added. After that, it is adjusted to an arbitrary pH, and the remainder of water is added to obtain a liquid detergent. At this time, from the viewpoint of suppressing the formation of gelation, it is preferable to start by blending optional components such as the (A) component and the (C) component as needed.

That is, as a method for producing the liquid detergent of the present invention,

Dispersing the component (A), the component (C), and other components as desired in a part of water;

Heating the solution in which the component is dispersed to the melting point of the component (B);

Adding the component (B) heated to the melting point to the heated solution;

Adjusting the pH of the solution obtained by adding the component (B); And

Adding the balance of the water to the pH-adjusted solution,

A method for producing a liquid cleaning liquid containing

<How to use>

The liquid detergent of the present invention can be used in the same manner as a conventional liquid detergent for medical use. For example, a method of injecting a liquid detergent into water together with the laundry when washing (usually washing), a method of directly applying a liquid detergent to a contaminated area such as mud or sebum contamination (application washing), a liquid detergent The method of dissolving in water beforehand and immersing the clothes (soaking washing), etc. are mentioned. Further, a method of applying a liquid detergent to the laundry, or immersing the clothing in a diluent of the liquid detergent and allowing it to stand appropriately, followed by washing in a washing machine, may be mentioned.

<action effect>

Since the liquid detergent of the present invention described above contains the component (A), the component (B) and the component (C), the cleaning power against hydrophobic contamination is high, and a structural liquid is formed. Accordingly, the liquid detergent of the present invention has thixotropic properties due to the structural liquid, and has a viscosity property of high viscosity in a state where a shear force is not applied and low viscosity in a state where a shear force is applied. That is, the liquid detergent of the present invention is highly viscous in a state in which no shearing force is applied, that is, in a state close to a stop, so that even if it is directly applied to adhered dirt such as clothing, it is difficult to penetrate into the clothing, and the liquid detergent tends to stay on the fabric. Therefore, the liquid detergent of the present invention can exhibit excellent coating and cleaning power.

In addition, the liquid detergent of the present invention has a low viscosity in a state in which a shearing force is applied, that is, a container in which the liquid detergent is stored is tilted, a liquid detergent is stirred, or a pressure is applied to the liquid detergent. Therefore, in the case of the liquid detergent of the present invention, it is easy to pour the liquid detergent in the container into the cap, and the discharging property from the cap to the inlet port of the washing machine and the discharging property from the inlet port are good, and it is excellent in usability.

Compound (A4) exhibits a high cleaning effect even if it is used in a small amount (low concentration). In addition, compared to other nonionic surfactants (such as general-purpose alcohol ethoxylates), it is difficult to adsorb to the object to be washed. In the present invention, by combining the compound (A4) and the component (B), it is difficult for the compound (A4) to adsorb to the object to be washed, so that the component (B) is more easily adsorbed preferentially. Therefore, it is estimated that the moisture content after washing and dehydration is more easily reduced by adsorption of the component (B), and a peculiar effect of providing a quick-drying property that the object to be washed easily dries is also expressed. Such an effect is particularly remarkable for the object to be washed containing chemical fibers such as acrylic fibers and polyester fibers.

In addition, since the liquid detergent of the present invention contains a surfactant at a high concentration, it is easy to hold the structural liquid, and is excellent not only in cleaning power in coating cleaning but also in cleaning power in ordinary cleaning. In addition, since the liquid detergent of the present invention has good cloth breaking during rinsing, it is also possible to reduce the number of rinsing cycles.

By the way, with respect to the cleaning agent, a product having a higher added value than before is required.

For example, water-soluble particles, such as capsules, perfumes or fabrics containing active ingredients instead of them to give sufficient fragrance to medical care after washing, or to scent even while wearing medical care, and beads to give unique product aesthetics, and Cleaners and the like have been developed containing water-insoluble particles. If it is a powder detergent, water-soluble particles or water-insoluble particles can be uniformly and stably dispersed, but in the case of a liquid detergent, water-soluble particles and water-insoluble particles are likely to float or settle, and it is difficult to uniformly disperse.

However, in the case of the liquid detergent of the present invention, since the structural liquid is formed, water-soluble particles and water-insoluble particles can be uniformly and stably dispersed.

As another aspect of the present invention,

It contains the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:

(A) component: selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) Nonionic surfactant containing at least one compound;

(B) component: at least one compound selected from the group consisting of a compound represented by the following general formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And,

(C) Component: Anionic surfactant;

[Formula 11]

(In formula (a-1), R ¹ is a C 9 to C 13 hydrocarbon group, R ² is a C ² to C 4 alkylene group, R ³ is a C 1 to C 4 alkyl group, m is the average of OR ² It is a number from 5 to 25 indicating the number of repetitions.)

[Formula 12]

(In formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s is a number of 5 to 20 representing the average repeat number of EO , t is a number of 1 to 4 representing the average repetition number of PO; [-(EO) _s -(PO) _t -] is the formula-(EO) _s -(PO) _t- It does not depend on the order, it indicates that it may be arranged in a mixture.)

[Formula 13]

(In formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p is an average repetition of A ¹ O Represents a number, q represents the average number of repetitions of A ² O, p>0, q>0, and p+q is a number of 10 or more and less than 60.)

[Formula 14]

(In formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group, a+b=7 to 19, c+d=7 to 19, and e+f=7 It is -19.);

Can be mentioned.

As another aspect of the present invention,

It contains the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:

(A) component: at least one compound selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) And a nonionic surfactant containing a compound represented by the following general formula (a-3);

(B) component: at least one compound selected from the group consisting of a compound represented by the above formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And

(C) Component: Anionic surfactant;

[Formula 15]

(In formula (a-3), R ⁵ is a C10-C22 hydrocarbon group, EO is an oxyethylene group, and n is a number of 5 to 20 representing the average repeat number of EO.);

Can be mentioned.

As another aspect of the present invention,

It contains the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) Nonionic surfactant containing a compound;

(B) component: compound (B1-1) represented by the following general formula (b1-1), compound (B1-2) represented by the following general formula (b1-2), and an alcohol having 6 or more and 18 or less carbon atoms At least one compound selected from the group consisting of; And

(C) Component: Anionic surfactant;

[Formula 16]

(Formula (of, Z ¹ ~Z ³ b1-1) is a hydroxy group, and a + b = 7~19, and is c + d = 7~19, e + f = 7~19.);

[Formula 17]

(Formula (b1-2) of the, Z ¹ ~Z ³ is a hydrogen atom, a + b = 7~19, c + d = 7~19 , and, e + f = 7~19.) ;

Can be mentioned.

As another aspect of the present invention,

It contains the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) Nonionic surfactant containing a compound;

(B) component: at least one compound selected from the group consisting of a compound represented by the above formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And

(C) component: Linear alkylbenzenesulfonic acid or its salt; Alkanesulfonic acid salts; Polyoxyethylene alkyl ether sulfuric acid ester salt; The number of carbon atoms obtained by adding an average of 0.5 to 10 moles of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) of an alkylene oxide having 2 to 4 carbon atoms Alkyl (or alkenyl) ether sulfuric acid ester salts having 10 to 20 linear or branched alkyl groups (or alkenyl groups); α-olefin sulfonate; And at least one anionic surfactant selected from the group consisting of higher fatty acid salts;

Can be mentioned.

As another aspect of the present invention,

It contains the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less based on the total mass of the liquid detergent:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant containing a compound and a compound represented by the formula (a-3);

(B) component: consisting of a compound (B1-1) represented by the formula (b1-1), a compound (B1-2) represented by the formula (b1-2), and an alcohol having 6 or more and 18 or less carbon atoms At least one compound selected from the group; And

(C) component: Linear alkylbenzenesulfonic acid or its salt; Alkanesulfonic acid salts; Polyoxyethylene alkyl ether sulfuric acid ester salt; The number of carbon atoms obtained by adding an average of 0.5 to 10 moles of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) of an alkylene oxide having 2 to 4 carbon atoms Alkyl (or alkenyl) ether sulfuric acid ester salts having 10 to 20 linear or branched alkyl groups (or alkenyl groups); α-olefin sulfonate; And at least one anionic surfactant selected from the group consisting of higher fatty acid salts;

Can be mentioned.

As another aspect of the present invention,

It contains at least one component selected from the group consisting of the following (A) component, the following (B) component, the following (C) component, water, urea, and clusterdextrin, and a component acceptable as a liquid detergent as desired, ,

Liquid detergent in which the sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less with respect to the total mass of the liquid detergent:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) A nonionic surfactant containing a compound and a compound represented by the formula (a-3);

(B) component: consisting of a compound (B1-1) represented by the formula (b1-1), a compound (B1-2) represented by the formula (b1-2), and an alcohol having 6 or more and 18 or less carbon atoms At least one compound selected from the group; And

(C) component: Linear alkylbenzenesulfonic acid or its salt; Alkanesulfonic acid salts; Polyoxyethylene alkyl ether sulfuric acid ester salt; The number of carbon atoms obtained by adding an average of 0.5 to 10 moles of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) of an alkylene oxide having 2 to 4 carbon atoms Alkyl (or alkenyl) ether sulfuric acid ester salts having 10 to 20 linear or branched alkyl groups (or alkenyl groups); α-olefin sulfonate; And at least one anionic surfactant selected from the group consisting of higher fatty acid salts;

Can be mentioned.

As another aspect of the present invention,

It is a liquid detergent containing the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

With respect to the total mass of the liquid detergent,

The sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less,

The component (A) is 1 to 70% by mass,

The component (B) is 0.1 to 10% by mass,

The component (C) is 1 to 20% by mass,

The water is 5 to 35% by mass, and

Liquid detergent in which the total amount of each component does not exceed 100% by mass:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) Nonionic surfactant containing a compound;

(B) component: at least one compound selected from the group consisting of a compound represented by the above formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And

(C) Component: Anionic surfactant;

Can be mentioned.

As another aspect of the present invention,

It is a liquid detergent containing the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

With respect to the total mass of the liquid detergent,

The sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less,

The component (A) is 1 to 70% by mass,

The component (B) is 0.1 to 10% by mass,

The component (C) is 1 to 20% by mass, and

The water is 5 to 35% by mass, and

The total amount of each component does not exceed 100% by mass;

The (C) component/(A) component, which is the mass ratio of the (C) component and the (A) component, is 0.02 to 0.7;

The (A) component/(B) component, which is a mass ratio of the (A) component and the (B) component, is 15 to 150,

Liquid cleaner:

(A) component: at least one selected from the group consisting of the compound represented by the formula (a-1), the compound represented by the formula (a-2), and the compound represented by the formula (a-4) Nonionic surfactant containing a compound;

(B) component: at least one compound selected from the group consisting of a compound represented by the above formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And

(C) Component: Anionic surfactant;

Can be mentioned.

As another aspect of the present invention,

It is a liquid detergent containing the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

With respect to the total mass of the liquid detergent,

The sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less,

The component (A) is 1 to 70% by mass,

The component (B) is 0.1 to 10% by mass,

The component (C) is 1 to 20% by mass, and

The water is 5 to 35% by mass, and

The total amount of each component does not exceed 100% by mass;

The (C) component/(A) component, which is the mass ratio of the (C) component and the (A) component, is 0.02 to 0.7;

The sum of the following compound (A1) and the following compound (A2) and the mass ratio of the following compound (A3), the sum of the compound (A1) and the compound (A2) / compound (A3) is 0.02 to 4.5

Liquid cleaner:

(A) component: with the compound (A1) represented by the formula (a-1), the compound (A2) represented by the formula (a-2), and the compound (A4) represented by the formula (a-4) A nonionic surfactant comprising at least one compound selected from the group consisting of, a compound (A3) represented by the formula (a-3), and;

(B) component: at least one compound selected from the group consisting of a compound represented by the above formula (b-1) and an alcohol having 6 or more and 18 or less carbon atoms; And

(C) Component: Anionic surfactant;

Can be mentioned.

As another aspect of the present invention,

It is a liquid detergent containing the following (A) component, the following (B) component, the following (C) component, water, and a component acceptable as a liquid detergent as desired,

With respect to the total mass of the liquid detergent,

The sum of the contents of all surfactants is 45% by mass or more and 80% by mass or less,

The component (A) is 1 to 70% by mass,

The component (B) is 0.1 to 10% by mass,

The component (C) is 1 to 20% by mass, and

The water is 5 to 35% by mass, and

The total amount of each component does not exceed 100% by mass;

The (C) component / (A) component, which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7,

Liquid cleaner:

(A) component: with the compound (A1) represented by the formula (a-1), the compound (A2) represented by the formula (a-2), and the compound (A4) represented by the formula (a-4) A nonionic surfactant comprising at least one compound selected from the group consisting of, a compound (A3) represented by the formula (a-3), and;

(B) component: consisting of a compound (B1-1) represented by the formula (b1-1), a compound (B1-2) represented by the formula (b1-2), and an alcohol having 6 or more and 18 or less carbon atoms At least one compound selected from the group; And

(C) component: Linear alkylbenzenesulfonic acid or its salt; Alkanesulfonic acid salts; Polyoxyethylene alkyl ether sulfuric acid ester salt; The number of carbon atoms obtained by adding an average of 0.5 to 10 moles of ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) of an alkylene oxide having 2 to 4 carbon atoms Alkyl (or alkenyl) ether sulfuric acid ester salts having 10 to 20 linear or branched alkyl groups (or alkenyl groups); α-olefin sulfonate; And at least one anionic surfactant selected from the group consisting of higher fatty acid salts.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[Used raw materials]

(A) As a component, the compound shown below was used.

A1-1: synthesized by adding 15 moles of ethylene oxide to MEE (methyl palm fatty acid (a mixture of methyl laurate/methyl myristolate = 8/2 by mass ratio) using an alkoxylation catalyst Nonionic surfactants, synthetic products). In the general formula (a-1), R ¹ is an alkyl group having 12 or 14 carbon atoms, R ² is an ethylene group, R ³ is a methyl group, and m is 15. It was synthesized as follows.

It was synthesized according to the synthesis method described in Japanese Patent Laid-Open No. 2000-144179 (corresponding to sample (D)). That is, the calcination obtained by sintering alumina and magnesium hydroxide (Kyowa Chemical Co., Ltd. product, "Kyowado 330") with a chemical composition of 2.5MgO·Al ₂ O ₃ ·nH ₂ O at 600°C for 1 hour in a nitrogen atmosphere. 2.2 g of alumina-magnesium hydroxide (unmodified) catalyst, 2.9 ml of 0.5N potassium hydroxide ethanol solution, 280 g of methyl laurate, and 70 g of myristate methyl ester were placed in a 4 L autoclave, and the catalyst was Modification was done. Subsequently, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining at a temperature of 180°C and a pressure of 3×10 5 Pa, 1052 g of ethylene oxide was introduced and reacted with stirring. Further, the reaction solution was cooled to 80°C, and 159 g of water and 5 g of activated clay and diatomaceous earth were added respectively as filtering aids, and then the catalyst was filtered off to obtain MEE.

A2-1: EOPO (nonionic surfactant in which an average of 9 moles of ethylene oxide, an average of 2 moles of propylene oxide, and an average of 9 moles of ethylene oxide are sequentially added to a primary alcohol of 10 to 14 carbon atoms) . The compound in which R ^{4 in} the general formula (a-2) is an alkyl group having 12 or 14 carbon atoms, s is 18, and t is 2.

-A3-1: LMAO-1 (nonionic surfactant in which ethylene oxide equivalent to an average of 15 moles was added to natural alcohol CO-1214 (manufactured by P&G)). It was synthesized as follows.

861.2 g of natural alcohol CO-1214 and 2.0 g of 30% NaOH aqueous solution were put into a pressure-resistant reaction vessel, and the inside of the vessel was replaced with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100°C and a pressure of 2.0 kPa or less, the inside of the container was heated to 160°C to obtain a reaction solution. Then, 760.6 g of ethylene oxide (gas state) was gradually added to the reaction solution while stirring the reaction solution. At this time, ethylene oxide was added to the blowing pipe while controlling the addition rate so that the reaction temperature did not exceed 180°C. After completion of the addition of ethylene oxide, the mixture was aged for 30 minutes at a temperature of 180°C and a pressure of 0.3 MPa or less, and then unreacted ethylene oxide was distilled off at a temperature of 180°C and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100°C or less, 70% by mass p-toluenesulfonic acid was added to neutralize the pH of the 1% by mass aqueous solution of the reactant to about 7 to obtain LMAO-1.

-A3-2: LMAO-2 (nonionic surfactant in which an average of 8 moles of ethylene oxide was added to natural alcohol CO-1214 (manufactured by P&G)). It was synthesized as follows.

LMAO-2 was obtained in the same manner as the synthesis method of LMAO-1, except that the amount of ethylene oxide introduced was changed to 507.4 g.

A4-1: Synthetic product of polyoxyethylene (20) hexadecylamine (corresponding to R ¹ = alkyl group having 16 carbon atoms, average repetition number of oxyethylene group 20, p+q = 20 in the general formula (a-4)) . In addition, A4-1 was synthesized as follows.

Fatty acid amine (manufactured by Tokyo Chemical Industry Co., Ltd., n-hexadecylamine) was put in an autoclave (manufactured by Daiatsu Choja Co., Ltd.), and the inside of the system was replaced with nitrogen, and then heated to 150°C to eliminate ethylene oxide. It was added in small portions until quantification was reached, thereby synthesizing a tertiary amine having an average added mole number of 2 moles of ethylene oxide (EO) (first step). Next, the obtained tertiary amine and an alkali catalyst (NaOH; 0.8 parts by mass, using 40% by mass NaOH aqueous solution based on 100 parts by mass of the tertiary amine) were placed in an autoclave, and the system was replaced with nitrogen, and heated. After dehydration under reduced pressure was performed, it was heated to 150°C, and ethylene oxide was added in small portions until a predetermined amount was reached, thereby obtaining A4-1 having an average added mole number of EO of 20 moles (second step). After the reaction, the product was neutralized with acetic acid. Moreover, it was 1121 when the molecular weight was calculated by amine value measurement.

A4-2: ethylene oxide (13 mol) propylene oxide (2 mol) adduct of stearylamine (R = alkyl group having 18 carbon atoms in the following general formula (A4-2), x + y = 2, a + b = 13) synthetic product. In addition, A4-2 was synthesized as follows.

[Formula 18]

Fatty acid amine (Lion Arczo Co., Ltd., Amine 18D) was placed in an autoclave (manufactured by Dai-Atsu Choja Co., Ltd.), the system was replaced with nitrogen, and then heated to 150°C, and propylene oxide was added in a small amount until the predetermined amount By each addition, a tertiary amine having an average added mole number of 2 moles of propylene oxide (PO) was synthesized (first step). Next, the obtained tertiary amine and an alkali catalyst (0.8 mass% by using 40 mass% NaOH aqueous solution) were put in an autoclave, the system was replaced with nitrogen, and dehydration by heating and reduced pressure was performed, and then 150°C. And ethylene oxide was added in small portions until a predetermined amount was reached, thereby obtaining a polyoxyalkylene stearylamine having an average added mole number of 2 moles and an average added mole number of EO 13 moles (step 2 Second). After the reaction, the product was neutralized with acetic acid. In addition, it was 939 when the molecular weight was calculated by measurement of the amine value.

(B) As a component, the compound shown below was used.

-B1-1: hydrogenated castor oil (made by Nichiyu Co., Ltd., 「Kastar Wax A Flakes」).

B1-2: Hydrogenated palm oil (manufactured by Shinnihon Ehwa Co., Ltd., 「Palm extremely hardened oil A」).

(C) As a component, the compound shown below was used.

C-1: LAS-H (straight-chain alkyl (carbon number 10-14) benzenesulfonic acid (manufactured by Lion Corporation, "Lyfon LH-200", 96% by mass pure)).

·C-2: Palm fatty acid (manufactured by Nichiyu Corporation).

C-3: Polyoxyalkylene alkyl ether sulfuric acid ester monoethanolamine salt (linear alkyl having 10 to 14 carbon atoms, PO average added mole number 1, EO average added mole number 3)

As an optional component, the compound shown below was used.

Common component a: It is shown in Table 1 below.

Common component b: It is shown in Table 2 below.

Common ingredient c: It is shown in Table 3 below.

Common ingredient d: It is shown in Table 4 below.

Common component e: It is shown in Table 5 below.

Common component f: It is shown in Table 6 below.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

Each compound contained in the common components a to f is as follows.

-Amidamine: dimethylaminopropylamide stearate (manufactured by Doho Chemical Industries, Ltd.), a cation surfactant.

PTS-H: Paratoluenesulfonic acid (Taika Co., Ltd. make, 「Teika Tox 300」).

· Benzoic acid Na: Sodium benzoate (manufactured by Dong-A Synthetic Co., Ltd.).

Citric acid: Citric acid (made by Ipbosha Oil Industry Co., Ltd.).

PEG: polyethylene glycol.

NaOH: sodium hydroxide

EtOH: Ethanol (95 specific alcohols also synthesized, manufactured by Nippon Alcohol Sales Co., Ltd.).

Ethanolamine: Monoethanolamine (made by Mitsui Chemical Co., Ltd.)

-Alkyl trimethyl ammonium salt: Dodecyl trimethyl chloride (manufactured by Lion Akzo Co., Ltd.), cation surfactant.

-Butylcarbitol: Butyldiglycol.

-Propylene glycol: 1,2-propanediol (manufactured by Dow Chemical).

· Cumene sulfonic acid Na: Cumene sulfonic acid sodium (Taikatox Co., Ltd. product, “Teikatox N5040”).

Coronase: Corona agent 48L (manufactured by Novozymes).

Silicone: Silicone emulsion (manufactured by Shin-Etsu Chemical Industries, Ltd., 「KM-98」).

Perfume A-1: Perfume composition a-1-1 described in Examples of Japanese Unexamined Patent Application Publication No. 2008-7872.

Perfume A-2: Perfume composition A described in Tables 11 to 18 of Japanese Unexamined Patent Publication No. 2002-146399.

-Fragment B-1: BLUEFLOWERPOP 「FFMHN2814」 (manufactured by Philmenihi).

·Fragment B-2: COSMICCAPS (manufactured by Jibodan).

-Fragment B-3: UNICAP503 (made by IFF).

Elements:: Reagents, manufactured by Junsei Chemical

Clusterdextrin: manufactured by Gurico Nutrition Foods Co., Ltd.

Water: purified water

[Examples 1 to 26, Comparative Examples 1 to 6]

By the production method shown below, the composition containing each component was adjusted to the content (mass %) shown in Tables 7-9. In addition, water (purified water) was used as a solvent, and components other than water shown in Tables 7 to 9 and water were combined to be 100% by mass. The content of water was taken as "balance".

<Production method>

(A) component and ethanol were put into a 500 mL beaker, and it stirred sufficiently with a magnet steer (made by MITAMURA KOGYO INC.). To this, optional components (excluding water and ethanol) and (C) component were added, water was added so that the total amount of this solution became 90% by mass relative to the total mass of the liquid detergent, and stirred again, and then (B ) It was warmed to the melting point of the component. To this, the component (B) heated to the melting point was added, and the mixture was stirred until the whole became uniform (that is, each component was uniformly dispersed). Subsequently, after adding an appropriate amount of a pH adjuster (sodium hydroxide or sulfuric acid) so that the pH at 25°C becomes 7.0, water was added so that the total amount of this solution became 100% by mass relative to the total mass of the liquid detergent, thereby obtaining a liquid detergent. .

For each of the obtained liquid detergents, coating cleaning power, usability, dispersibility, and quick-drying properties were evaluated by the following evaluation methods. The results are shown in Tables 7-9.

<Evaluation method>

(Evaluation of cleaning power)

500 g of spinach was washed, and a portion of the root was removed. 250 ml of 3DH hard water was put into a mixer (National Soup & Fruit MX-V350), and spinach was added in small portions and pulverized. After putting all the spinach in the mixer, it was rotated for 5 minutes, and it was completely juiced.

A beaker was placed in an ice bath, a colander was placed thereon, and a gauze of 6 layers was placed thereon, and the spinach juice obtained previously was filtered. At this time, when the gauze was clogged, the gauze was replaced. The filtrate was transferred to a vat (29×22×4cm), 10 sheets of cotton cloth (#100 26×21cm) were put, and immersed for 3 minutes while turning occasionally.

The cotton cloth was taken out from the bat, and left overnight (1 晩), turning the cloth upside down every 20 to 30 minutes. Thereafter, rinsed for 2 minutes with a washing machine (manufactured by Mitsubishi Electric Corporation, ``CW-C30A1-H''), dehydrated for more than 30, air-dried and stored in a dark place, and a cloth contaminated with spinach (contaminated cloth) was used. .

Subsequently, 0.1 g of a liquid detergent after storage at 15° C. for 24 hours was applied to each of ten contaminated cloths (0.1 g of a liquid detergent/one contaminated cloth), and left for 5 minutes. Thereafter, the stained cloth and a commercial T-shirt (100% cotton, manufactured by B.V.D.) were put into a washing tester (Terg-O-Tometer, manufactured by UNITED STATES TESTING). In addition, the amount of the T-shirt added was adjusted so that the mass of the entire fabric was about 45 g.

According to the standard course of the washing tester, one washing operation was performed in which washing 10 minutes, rinsing 2 times, and dehydration 3 minutes were sequentially performed.

The contaminated cloth after the washing operation was left in a constant temperature and humidity room at 25°C and a humidity of 65% RH for 24 hours to dry the contaminated cloth.

The b-value (reflectance) of the original fabric before spinach contamination, the spinach-contaminated fabric (contaminated cloth) before washing, and the contaminated cloth after washing and drying are measured using a colorimeter (manufactured by Nippon Denshoku Co., Ltd., product name: SE2000). It was measured, and the coating cleaning power (%) against spinach contamination was calculated by the following formula (1).

Coating cleaning power (%) = (b value of contaminated cloth after washing and drying-b value of contaminated cloth before washing) / (b value of original cloth-b value of contaminated cloth before washing) × 100 ... (One)

In the evaluation of the coating cleaning power against spinach contamination, it was determined that the coating cleaning power was good if it was C, B, A in the following evaluation criteria using the coating cleaning power (%) calculated by the top formula.

. In addition, for coating cleaning power (%), the average score of 10 soiled cloth sheets was used.

A: The cleaning rate is 90% or more.

B: The cleaning rate is 85% or more and less than 90%.

C: The cleaning rate is 80% or more and less than 85%.

D: The cleaning rate is less than 80%.

(Evaluation of usability)

A bottle (200 ml in volume) containing 400 g of a liquid detergent was left in a constant temperature bath at 25°C. After 3 hours had elapsed, the bottle was taken out from the thermostat, the bottle was tilted, and the contents (liquid detergent) were poured into the transparent cap.

Ease of pouring when pouring the liquid detergent into the cap was evaluated by 10 panelists, and scored according to the following criteria. The average score of the scores of 10 people was classified according to the following evaluation criteria, and usability was evaluated, and if it was C, B, and A, usability was determined to be good.

Judgment Criteria:

1: The ease of pouring is very poor compared to Comparative Example 2.

2 points: The ease of pouring was slightly worse than that of Comparative Example 2.

3 points: Equivalent to Comparative Example 2 or Comparative Example 2.

4 points: The ease of pouring is slightly better than that of Comparative Example 2.

5 points|pieces: The ease of pouring is very good compared with Comparative Example 2.

Evaluation standard :

A: Average score of 4.5 or more.

B: Average score of 4.0 or more and less than 4.5.

C: An average score of 3.5 or more and less than 4.0.

D: Average score is less than 3.5 points.

(Evaluation of dispersibility)

30 g of a liquid detergent was filled in a 100 ml glass bottle (light bulb size bottle: PS-No6), and 0.5 g of beads (manufactured by Toshiki Pigment Co., Ltd., "PFL-RED 7155T Lot. 0308") was added and dispersed. After storing in a constant temperature bath at 25° C. for 1 day, the glass bottle was taken out from the thermostat, and the state of dispersion of the beads in the liquid detergent was visually checked, and evaluated according to the following evaluation criteria.

A: Beads are uniformly dispersed in the liquid detergent.

B: Beads are floating or sinking.

<Evaluation of quick-drying performance>

As the evaluation fabric, a commercial shirt (Heat Tech manufactured by Unicro Co., Ltd. clothing display composition: 40% acrylic, 33% polyester, 21% rayon, 6% polyurethane) was passed through.

(1) Pre-treatment of evaluation cloth

In a fully automatic washing machine (product name AW-80VC manufactured by Toshiba Corporation), 34 liters of tap water at 60°C was put. There, 30 g of a medical detergent (trade name blue diamond manufactured by Lion Corporation) was added thereto, and the commercially available shirt was then placed. Subsequently, a washing operation in which washing 15 minutes, rinsing 3 times, and spin-drying 7 minutes were sequentially performed by the standard course of the fully automatic washing machine was repeated twice. Next, the washing operation as described above was repeated three times without adding a medical detergent. Thereafter, it was naturally dried and used as an evaluation cloth.

(2) Quick-drying test

In a fully automatic washing machine (product name AW-80VC manufactured by Toshiba Corporation), 34 liters of tap water at 15°C was put. There, the three evaluation cloths, T-shirt (100% cotton) and cotton towel (100% cotton) were added (the amount of T-shirt and cotton towel input was determined before the three evaluation cloths, T-shirt and cotton towel). It was adjusted so that the mass was 1.7 kg).

10 g of the liquid detergent of each example was added thereto, and one washing operation was performed in which 10 minutes of washing, one rinsing, and 3 minutes of dehydration were sequentially performed according to the standard course of the fully automatic washing machine.

Subsequently, the evaluation fabric was dried in a constant temperature room (model made by ESPEC CORP: TBR-2HAOPX) having a temperature of 25°C and a relative humidity of 60%.

At this time, the mass after drying with time was measured, and this was taken as the weight after drying. The moisture content of the evaluation fabric was tracked with time, and the moisture content 1 hour after drying was measured.

(3) Evaluation of quick-drying performance

The moisture content (%) was calculated based on the following formula.

Moisture content (%) = (weight after drying over time (g)-initial weight (g)) / weight after drying over time (g) × 100

In the evaluation of the quick-drying performance, the moisture content (%) calculated by the upper equation was used, and when the moisture content of Comparative Example 3 1 hour after drying was set to 1, the relative moisture content in each example was calculated,

Evaluation was performed based on the following criteria, and if it was B and A, it was judged that the quick-drying performance was good.

A: For Comparative Example 3, the relative moisture content was 0.3 or less

B: For Comparative Example 3, the relative moisture content was 0.4 or more and 0.6 or less

C: For Comparative Example 3, the relative moisture content was 0.7 or more and 0.9 or less

D: For Comparative Example 3, the relative moisture content was 1.0 or more

[Table 7]

[Table 8]

[Table 9]

As is clear from Tables 7 and 8, the liquid detergent obtained in each example was excellent in coating cleaning power and excellent usability.

In addition, the liquid detergent obtained in each Example could also disperse beads uniformly. From this result, it is considered that the liquid detergent obtained in each example forms a structural liquid.

On the other hand, as is clear from Table 9, the liquid detergent of Comparative Example 1, which does not contain the component (A) and whose total surfactant content is 9% by mass, is inferior in coating cleaning power and usability.

The liquid detergent of Comparative Example 2 that does not contain the component (A) is inferior in usability.

The liquid detergent of Comparative Example 3 which does not contain the component (B) is inferior in coating cleaning power and usability.

The liquid detergent of Comparative Example 4 in which the total surfactant content was 39% by mass was inferior in coating cleaning power and usability.

The liquid detergent of Comparative Example 5 which does not contain the component (C) is inferior in usability.

In addition, in the case of Comparative Examples 2 to 5, the beads could not be uniformly dispersed. Therefore, it is considered that the liquid detergents of Comparative Examples 2 to 5 formed spherical micelles without forming a structural liquid.

[Industrial availability]

The present invention is extremely effective industrially because it is possible to provide a liquid detergent excellent in coating cleaning power and also excellent in usability.

Claims (3)

A liquid characterized in that the following (A) component, (B) component, and (C) component are contained, and the sum of the contents of all surfactants is 45 mass% or more and 80 mass% or less with respect to the total mass of the liquid detergent Cleaning agent:
(A) component: selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), and a compound represented by the following general formula (a-4) Nonionic surfactant containing at least one compound;
(B) component: A compound represented by the following general formula (b-1); And
(C) Component: Anionic surfactant;
[Formula 1]

(In formula (a-1), R ¹ is a C 9 to C 13 hydrocarbon group, R ² is a C ² to C 4 alkylene group, R ³ is a C 1 to C 4 alkyl group, m is the average of OR ² It is a number from 5 to 25 indicating the number of repetitions.)
[Formula 2]

(In formula (a-2), R ⁴ is a hydrocarbon group having 10 to 20 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, and s is a number of 5 to 20 representing the average repeat number of EO , t is a number of 1 to 4 representing the average repetition number of PO; [-(EO) _s -(PO) _t -] is the formula-(EO) _s -(PO) _t- It indicates that it may be arranged in a mixture regardless of the order.)
[Formula 3]

(In formula (a-4), R ¹ is a hydrocarbon group having 10 to 20 carbon atoms; A ¹ O and A ² O are each independently an oxyalkylene group having 2 to 4 carbon atoms; p is an average repetition of A ¹ O Represents the number, q represents the average repetition number of A ² O, p>0, q>0, p+q is a number of 10 or more and less than 60.)
[Formula 4]

(In formula (b-1), Z ^{1 to} Z ³ are each independently a hydrogen atom, a hydroxy group, or a carboxyl group, a+b=7 to 19, c+d=7 to 19, and e+f=7 It is ∼19.) The method of claim 1,
A liquid detergent characterized in that the (C) component/(A) component, which is a mass ratio of the (C) component and the (A) component, is 0.02 to 0.7. The method of claim 1,
With respect to the total mass of the liquid detergent, the content of (A) is 1 to 70 mass%, the content of the component (B) is 0.1 to 10 mass%, and the content of the component (C) is 1 to Liquid detergent, characterized in that 20% by mass.