WO2012137642A1

WO2012137642A1 - Liquid detergent

Info

Publication number: WO2012137642A1
Application number: PCT/JP2012/058126
Authority: WO
Inventors: 神藤　宏明; 貴行黒川; 弘嗣小倉
Original assignee: ライオン株式会社
Priority date: 2011-04-01
Filing date: 2012-03-28
Publication date: 2012-10-11
Also published as: JP5789394B2; KR20140003569A; CN103459579A; JP2012214653A; CN103459579B; MY161693A

Abstract

A liquid detergent which contains 40% by mass or more of (A) a surfactant, 150 ppm or less (on a mass basis) of (B) a dye, and 0.5-12% by mass of (C) urea or a derivative thereof.

Description

Liquid cleaning agent

The present invention relates to a liquid detergent containing urea.
This application claims priority based on Japanese Patent Application No. 2011-081768 filed in Japan on April 1, 2011, the contents of which are incorporated herein by reference.

Recently, as a detergent used for laundry at home, it has features that are different from powder detergents (for example, there is no undissolved, you can enjoy fragrance, etc.), and the price is affordable, so the demand for liquid detergents has increased. ing.
With regard to liquid detergents, there are consumer complaints such as "It is heavy to hold a container with liquid detergent by hand", "It is difficult to take home from a store", "It will be used up quickly".
On the other hand, in the field of cleaning agents, due to heightened awareness of environmental impact, the amount of cleaning agent used per wash is reduced, and the size of the container in which the cleaning agent is stored is reduced to reduce the amount of resin waste. That is required.
In response to such dissatisfaction and demand, the composition of the liquid cleaning agent is a so-called “concentrated type” that contains a high concentration of surfactant and can be washed with half the amount of conventional use per wash. Compositions have been developed.

The liquid detergent having a high surfactant content has a problem that the usability deteriorates with the passage of time, particularly because the liquid detergent itself tends to gel on the liquid surface. If the liquid cleaning agent is gelled, it becomes difficult to measure the liquid cleaning agent in the cap (that is, metering), and the ability to discharge the cap from the cap to the inlet of the washing machine also deteriorates. For this reason, in addition to a high detergency, the concentrated liquid detergent is required to maintain fluidity without causing gelation or the like with time and to have good liquidity.
On the other hand, a concentrated liquid cleaning agent using a specific polyoxyethylene fatty acid methyl ester as a surfactant is disclosed (see Patent Documents 1 and 2).

Also, when measuring the liquid detergent into the cap, in the case of a liquid with a colorless and transparent appearance, it is difficult to collate with the scale of the cap, so the amount of liquid measured in the cap is likely to be too much or too little than the predetermined amount. . In particular, in the case of a concentrated liquid cleaning agent, it is important to accurately measure and use the cap because it can be used in a smaller amount than in the past.
In order to solve these problems, the liquid cleaning agent is colored by coloring it, and the cap is made transparent so that the amount of liquid cleaning agent collected in the cap can be easily understood and measured. .

JP 2008-7706 A JP 2008-7707 A

However, in a concentrated liquid cleaning agent containing a pigment, the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a whole day or night, or the rinsing is insufficient. There is a problem that pigments are likely to be dyed on an object to be washed.
The present invention has been made in view of the above circumstances, and in a concentrated liquid detergent containing a pigment, the liquid detergent has a high detergency and has suppressed dye dyeing on an object to be washed. The issue is to provide.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems. That is, in the first aspect of the present invention, the surfactant (A) is 40% by mass or more, the dye (B) is 150 ppm (mass basis) or less, and urea or its derivative (C) is 0.5 to 12% by mass. And a liquid detergent containing
According to a second aspect of the present invention, in the liquid detergent of the first aspect, the surfactant (A) is a nonionic surfactant represented by the following general formulas (a1) to (a3): It is a liquid detergent containing at least one selected surfactant.

[In the formula (a1), R ¹ is a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon An alkyl group having a number of 1 to 4, s represents an average number of repetitions of OR ² and an integer of 5 to 30; in the formula (a2), R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms; R ⁵ represents an alkylene group having 2 to 4 carbon atoms, t represents an average number of repetitions of R ⁵ O, and is an integer of 5 to 20; in formula (a3), R ⁶ represents an alkyl having 10 to 16 carbon atoms A group or an alkenyl group, p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0 , 0 <q ≦ 3, and p + r = 10-30, EO is an oxyethylene group, PO is an oxyp Represents a pyrene group, it may be arranged in a mixed manner and EO and PO in (EO) p / (PO) q. ]

Further, a third aspect of the present invention is a liquid detergent further comprising an organic solvent (D) represented by the following general formula (d1) in the liquid detergent of the first or second aspect.

[Wherein R ⁷ represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms; m represents an average repeat number of PO, n represents an average repeat number of EO, and m represents an integer of 0 to 2] N is an integer of 0 to 3 and 1 ≦ m + n ≦ 5; EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

According to the present invention, it is possible to provide a liquid cleaning agent that has high detergency and suppresses dye dyeing on an object to be washed in a concentrated liquid cleaning agent containing a dye.

The liquid detergent of the present invention contains 40% by mass or more of the surfactant (A), 150 ppm (mass basis) or less of the dye (B), and 0.5 to 12% by mass of urea or its derivative (C). To do.
Hereinafter, these three components may be referred to as (A) component, (B) component, and (C) component, respectively.

[Surfactant (A)]
As surfactant (A), nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, and other surfactants usually used in liquid detergents for clothing are blended. Can do.

(Nonionic surfactant)
Preferred examples of the nonionic surfactant include surfactants represented by the following general formulas (a1) to (a3), and polyoxyalkylene alkyl ethers.

[In the formula (a1), R ¹ is a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, and R ³ is carbon An alkyl group having a number of 1 to 4, and s represents an average number of repetitions of OR ² and is an integer of 5 to 30. ]

In the formula (a1), R ¹ is a linear or branched alkyl group having 5 to 21 carbon atoms, or a linear or branched alkenyl group having 5 to 21 carbon atoms.
The number of carbon atoms of the alkyl group and alkenyl group in R ¹ is preferably 9 to 13 carbon atoms, more preferably 11 to 13 carbon atoms, respectively, from the viewpoint of improving detergency and storage stability.
Specific examples of the alkyl group include C ₁₁ H ₂₃ , C ₁₃ H ₂₇ , and the like.
Specific examples of the alkenyl group include C ₁₁ H ₂₁ , C ₁₃ H ₂₅ , and the like.
R ² is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In addition, (OR ² ) s may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.
R ³ is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

In the formula (a1), s represents an average number of repetitions of OR ² and is an integer of 5 to 30. From the viewpoint of improving the detergency and liquid stability of the liquid detergent (especially stability at low temperatures, etc.), s is preferably 12-18.

In the component represented by the formula (a1), it is preferable that a narrow ratio indicating a distribution ratio of compounds having different OR ² repeating numbers is 20% by mass or more. The upper limit of the narrow ratio is preferably substantially 80% by mass or less. That is, the narrow ratio is preferably 20 to 80% by mass, more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass. As the narrow ratio is higher, better detergency can be obtained. However, if it is too high, the temporal stability at low temperatures may be lowered.
In this specification, the “narrow ratio” refers to a value represented by the following mathematical formula (S).

In the formula (S), S _max represents the number of added moles of alkylene oxide of the alkylene oxide adduct most frequently present in the whole component represented by the formula (a1).
i represents the number of added moles of alkylene oxide. Yi represents the proportion (% by mass) of the alkylene oxide adduct having an added mole number of alkylene oxide present in the whole component represented by the formula (a1).
The narrow rate can be controlled by the method for producing the component represented by the formula (a1).

The method for producing the component represented by the formula (a1) is not particularly limited, and as an example, a method of adding an alkylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (special feature). (See Japanese Laid-Open Patent Publication No. 2000-144179).
As a suitable example of such a surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , surface-modified with a metal hydroxide or the like, A composite metal oxide catalyst such as magnesium oxide to which Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) are added; and at least one compound selected from the group consisting of metal hydroxides, metal alkoxides, etc. Examples thereof include a calcined product catalyst of modified hydrotalcite. In the surface modification of the composite metal oxide catalyst, a mixing ratio of the composite metal oxide and at least one compound selected from the group consisting of a metal hydroxide and a metal alkoxide is used. The ratio of at least one compound selected from the group consisting of metal hydroxides and metal alkoxides to 100 parts by mass is preferably 0.5 to 10 parts by mass, and preferably 1 to 5 parts by mass. Is more preferable.

[In the formula (a2), R ⁴ represents a hydrocarbon group having 10 to 22 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms, t represents an average number of repeating R ⁵ O, and 5 to It is an integer of 20. ]

In the formula (a2), R ⁴ has 10 to 22, preferably 10 to 20, more preferably 10 to 18 carbon atoms. The hydrocarbon group for R ⁴ may be linear or branched, and may have an unsaturated bond. Specific examples of the hydrocarbon group for R ⁴ include C ₁₀ H ₂₁ , C ₁₂ H ₂₅ , C ₁₄ H ₂₉ , C ₁₆ H ₃₃ , C ₁₈ H ₃₇ , C ₂₀ H ₄₁ , and the like.
The component represented by the formula (a2) may be a component having a single chain length or a mixture of components having a plurality of chain lengths. As raw materials for synthesizing the component represented by the formula (a2), alcohols derived from natural fats and oils such as palm oil, palm oil and beef tallow; synthetic alcohols derived from petroleum and the like can be used.
In the formula (a2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. (R ⁵ O) t may be a single oxyalkylene group repeating structure, or two or more oxyalkylene groups may be mixed. When two or more kinds of oxyalkylene groups are mixed, the oxyalkylene groups may be added in a block shape or may be added in a random shape.

In the formula (a2), t represents an average number of repetitions of R ⁵ O and is an integer of 5 to 20, preferably an integer of 8 to 18, more preferably an integer of 10 to 16. When t exceeds 20, the HLB becomes too high and disadvantageous for the sebum cleaning, so that the cleaning function tends to deteriorate. When t is 5 or more, it becomes easy to prevent odor deterioration. In particular, when t is in the range of 10 to 16, it exhibits a high detergency against sebum dirt.

The addition mole number distribution of R ⁵ O varies depending on the reaction method during the production of the component represented by the formula (a2), and is not particularly limited. For example, when alkylene oxide is added to a hydrophobic group raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide, the added mole number distribution of R ⁵ O tends to be a relatively wide distribution. is there. Also, specific alkoxylation such as magnesium oxide added with metal ions such as Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc. described in JP-B-6-15038 When an alkylene oxide is added to a hydrophobic group raw material using a catalyst, the added mole number distribution of R ⁵ O tends to be a relatively narrow distribution.

As a specific example of the component represented by the formula (a2), a trade name Neodol manufactured by Shell (mixture of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms: hereinafter may be referred to as C12 / C13), A component obtained by adding 12 or 15 moles of ethylene oxide to an alcohol such as Safol 23 (C12 / C13) manufactured by Sasol; 9, 12 relative to a natural alcohol such as trade names CO-1214 or CO-1270 manufactured by P & G Or a component added with 15 moles of ethylene oxide; a component added with 9, 12 or 15 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms (manufactured by Nippon Shokubai Co., Ltd., Softanol 90, 120 or 150).

[In the formula (a3), R ⁶ represents an alkyl group or alkenyl group having 10 to 16 carbon atoms; p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, and r represents the average number of repetitions of EO. P, q, r are integers satisfying p> 1, r ≧ 0, 0 <q ≦ 3, and p + r = 10 to 30; EO represents an oxyethylene group, PO represents an oxypropylene group, EO and PO in (EO) p / (PO) q may be mixed and arranged. ]

In the formula (a3), the alkyl group or alkenyl group in R ⁶ has 10 to 16 carbon atoms, and preferably 10 to 14 carbon atoms. The alkyl group and alkenyl group of R ⁶ may be linear or branched.
Specific examples of the linear or branched alkyl group include C ₁₀ H ₂₁ , C ₁₂ H ₂₅ , C ₁₄ H ₂₉ , and the like.
Specific examples of the linear or branched alkenyl group include C ₁₀ H ₁₉ , C ₁₂ H ₂₃ , C ₁₄ H ₂₇ , and the like. In the formula (a3), r is r ≧ 0, preferably r ≧ 1. p + r = 10 to 30, preferably p + r = 14 to 20.
In the formula (a3), the ratio of EO and PO is preferably a ratio represented by q / (p + r) of 0.1 to 0.5, more preferably 0.1 to 0.3. is there. When the ratio represented by q / (p + r) is equal to or greater than the lower limit value, bubbles are not excessively formed and foaming is optimized. When the ratio represented by q / (p + r) is not more than the upper limit value, an appropriate viscosity is easily obtained, and gelation is easily suppressed. Moreover, biodegradability improves because q is 3 or less.
Only one of EO and PO in (EO) p / (PO) q may exist, or they may be mixed and arranged. In (EO) p / (PO) q, EO and PO may be added randomly, or may be added in blocks.

The component represented by the formula (a3) can be synthesized by a known method. As an example, after addition reaction of ethylene oxide and propylene oxide in this order to alcohol derived from natural fats and oils or after mixed addition of ethylene oxide and propylene oxide (random addition), ethylene oxide is added again by adding ethylene oxide and propylene oxide. The component represented by the formula (a3) can be synthesized.

As the polyoxyalkylene alkyl ether, an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms is added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Polyoxyalkylene alkyl ether or polyoxyalkylene alkenyl ether (alcohol alkoxylate) may be mentioned. Among these, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene polyoxypropylene alkenyl ether are preferable.
Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. The alkyl group of the aliphatic alcohol may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.

(Anionic surfactant)
Anionic surfactants include alkylbenzene sulfonate, alkyl sulfate, secondary alkane sulfonate, polyoxyethylene alkyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid ester salt, polyoxyethylene alkyl Examples include ether carboxylates.
Specific examples of the anionic surfactant include a linear alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 16 carbon atoms (preferably 10 to 14 carbon atoms); an alkyl group having 10 to 20 carbon atoms. Alkyl sulfate (AS): Polyalkylene having an alkyl group having 10 to 20 carbon atoms (preferably 10 to 14 carbon atoms) and having an average addition mole number of ethylene oxide of 1 to 10 (preferably an average addition mole number of 1 to 4). Oxyethylene alkyl ether sulfate (AES); α-olefin sulfonate (AOS) having an alkyl group having 10 to 20 carbon atoms; two having an alkyl group having 10 to 20 carbon atoms (preferably 10 to 14 carbon atoms) Secondary alkanesulfonate (SAS); α-sulfo fatty acid methyl ester salt having an alkyl group having 10 to 20 carbon atoms (α-SF); It has 0 alkyl group, a polyoxyethylene alkyl error of average addition mole number of 1 to 10 ethylene oxide - Terukarubon acid salts, and the like preferably.
Examples of these salts include alkali metal salts such as sodium salts and potassium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts, and alkali metal salts are preferred.

As the polyoxyethylene alkyl ether sulfate, when the addition mole number of ethylene oxide of the ethylene oxide adduct most present on the mass basis in all ethylene oxide adducts constituting the polyoxyethylene alkyl ether sulfate is “nlmax”, Polyoxyethylene alkyl ether sulfates in which the total proportion of ethylene oxide adducts with the number of moles of ethylene oxide added (nlmax-1), nlmax, and (nlmax + 1) is 55% by mass or more based on the total ethylene oxide adduct Polyoxyethylene alkyl ether sulfate in the range of 55 to 80% by mass is more preferable. Within the above range, the fluidity of the polyoxyethylene alkyl ether sulfate is increased and the manufacturability is improved.

Among the above, as the anionic surfactant, alkylbenzene sulfonate, polyoxyethylene alkyl ether sulfate, and secondary alkane sulfonate are preferable because of good anti-recontamination property; alkylbenzene sulfonic acid Salts and polyoxyethylene alkyl ether sulfates are more preferred; alkyl benzene sulfonates are particularly preferred.

Examples of the cationic surfactant include alkylamine salts and alkyl quaternary ammonium salts.
Examples of amphoteric surfactants include carboxylic acid type amphoteric surfactants (amino type and betaine type), sulfate ester type amphoteric surfactants, sulfonic acid type amphoteric surfactants, and phosphate ester type amphoteric surfactants. It is done.
Examples of other surfactants include natural surfactants, protein hydrolyzate derivatives, polymer surfactants, surfactants containing titanium / silicon, and fluorocarbon surfactants.

(A) A component may be used individually by 1 type and may use 2 or more types together.
Among the above, it is preferable to use a nonionic surfactant and an anionic surfactant as the component (A).
In particular, the component (A) preferably contains 50% by mass or more of the nonionic surfactant relative to the component (A), more preferably contains 80% by mass or more of the nonionic surfactant. It is more preferable to contain 90% by mass or more of the ionic surfactant, and the nonionic surfactant may be 100% by mass.
By using a nonionic surfactant, it is easy to obtain a concentrated liquid cleaning agent that does not cause gelation even if it contains a high concentration of surfactant and exhibits good storage stability. In addition, when the liquid cleaning agent is a concentrated type liquid cleaning agent, an excellent application cleaning power can be obtained when the liquid cleaning agent is applied to an object to be cleaned.
The nonionic surfactant contains at least one nonionic surfactant selected from the nonionic surfactants represented by the general formulas (a1) to (a3) because of its high detergency. Is preferred.
In addition, as the component (A), an antiionic surfactant is used in combination with a nonionic surfactant because the antifouling property of preventing dirt from adhering to the washing object again in the washing liquid is increased. Is preferred.

The content of the component (A) in the liquid detergent is 40% by mass or more, preferably 40 to 70% by mass, and preferably 45 to 65% by mass with respect to the total mass of the liquid detergent. More preferred.
When the content of the component (A) is 40% by mass or more with respect to the total mass of the liquid detergent, the effect of the present invention is remarkably exhibited. In addition, good detergency can be obtained. In addition, since it contains a high-concentration surfactant, the effectiveness (commercial value) as a concentrated liquid cleaning agent is increased.
When the content of the component (A) is preferably 70% by mass or less, more preferably 65% by mass or less, with respect to the total mass of the liquid detergent, the gelation of the liquid detergent on the liquid surface with time Etc. are less likely to occur, and a film is less likely to be formed on the liquid surface.

When an anionic surfactant is used in combination with a nonionic surfactant, the content of the anionic surfactant is preferably 1 to 10% by mass, more preferably 1 to 5% by mass with respect to the total mass of the liquid detergent. Preferably, 2 to 5% by mass is more preferable.
When the content of the anionic surfactant is 10% by mass or less with respect to the total mass of the liquid detergent, the liquid detergent itself is difficult to gel and a film is formed on the liquid surface of the liquid detergent. It becomes difficult. Further, the coating cleaning power is improved satisfactorily. When the content of the anionic surfactant is 1% by mass or more based on the total mass of the liquid detergent, the recontamination preventing property is further improved.

[Dye (B)]
The dye (B) is not particularly limited, and is an acid dye, basic dye, cationic dye, mordant (oil-soluble) dye, vat dye, naphthol dye (azo dye), reactive dye (reactive dye), disperse dye, An oxidation dye etc. are mentioned. The structure of each dye is described in the “Legal Handbook” (edited by Japan Cosmetic Industry Association).
Among the above, as the component (B), a dye having a maximum absorption wavelength at 400 to 700 nm is preferable, and a dye having a maximum absorption wavelength at 500 to 700 nm is more preferable because the effects of the present invention are remarkably easily exhibited. A blue to green dye having a maximum absorption wavelength at 590 to 650 nm is particularly preferable.
Specific examples of the dye (B) include the following blue dyes and green dyes.

Blue dye: C.I. I. Acid Blue 5, C.I. I. Acid Blue 9, C.I. I. Acid Blue 74, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 63, C.I. I. Diverse Blue1, C.I. I. Diverse Blue 3, C.I. I. Diverse Blue 5, C.I. I. Diverse Blue 6, C.I. I. Diverse Blue 7, C.I. I. Diverse Blue 26, C.I. I. Diverse Blue 27, C.I. I. Diverse Blue 54, C.I. I. Diverse Blue 55, C.I. I. Diverse Blue 56, C.I. I. Diverse Blue 60, C.I. I. Diverse Blue 61, C.I. I. Diverse Blue 62, C.I. I. Diperse Blue 64, C.I. I. Diverse Blue 72, C.I. I. Diverse Blue 73, C.I. I. Diverse
Blue 81, C.I. I. Diverse Blue87, C.I. I. Diverse Blue90, C.I. I. Diverse Blue 91, C.I. I. Diverse Blue 97, C.I. I. Diverse Blue 98, C.I. I. Diverse Blue99, C.I. I. Diverse Blue 103, C.I. I. Diverse Blue 104, C.I. I. Diverse Blue 105, C.I. I. Basic Blue 7, C.I. I. Vat Blue1, C.I. I. Vat Blue 6, C.I. I. Pigment Blue 15 etc.
Also, among the above-described Solvent (oil-soluble) dyes, dyes that are chemically modified with a water-soluble polymer such as polyethylene glycol or polypropylene glycol at the end of the chromophore structure to increase water solubility. But you can. Specific examples include trade names such as Liquid Blue Blue and Liquid Blue BL manufactured by Milliken.

Green dye: C.I. I. Acid Green1, C.I. I. Acid Green 3, C.I. I. Acid Green 5, C.I. I. Acid Green 25, C.I. I. Food
Blue2, C.I. I. Food Green 3, C.I. I. Solvent Green 3, C.I. I. Food Green 3, C.I. I. Solvent Green 7, C.I. I. Solvent Green et al.

(B) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (B) in the liquid detergent is 1 ppm (mass basis) or more and 150 ppm (mass basis) with respect to the total mass of the liquid detergent, from the dyeing property to the washing object and the liquid color degree by blending. (Mass basis) or less (0.015 mass% or less), preferably 1 to 100 ppm (mass basis) (0.0001 to 0.01 mass%), preferably 3 to 50 ppm (mass basis) (0.0003 to 0.003). (005% by mass) is more preferable.
If the content of the component (B) is less than the lower limit, the liquid detergent liquid may not be sufficiently colored. On the other hand, when the content of the component (B) exceeds the upper limit value, dye dyeing to the object to be washed may not be suppressed.

[Urea or its derivative (C)]
Examples of urea or its derivative (C) include urea [CO (NH ₂ ) ₂ ], urea double salt, and other urea derivatives.
Examples of the urea double salt include 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 to 6) 4CO (NH ₂ ) ₂ · 2H ₂ O or the like can be used.

In the present invention, the “urea derivative” includes a compound having a structure represented by the following general formula (c1). Among the urea derivatives, preferred are compounds represented by the general formula (c1-1).

In the formula (c1-1), 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.
Examples of the compound represented by the formula (c1-1) include 1,3-dimethylurea, N- (2-hydroxyethyl) urea and the like.

As the component (C), one type may be used alone, or two or more types may be used in combination.
The content of the component (C) in the liquid detergent is preferably 0.5 to 12% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 8% with respect to the total mass of the liquid detergent. % By mass.
When the content of the component (C) is less than the lower limit, dyeing of the object to be washed may not be sufficiently suppressed. On the other hand, when the content of the component (C) exceeds the upper limit value, ammonia tends to be generated as a decomposition product after storage, and odor may be a problem as a liquid detergent product. Moreover, since the affinity to dirt is likely to be reduced, there is a possibility that the coating cleaning power is reduced.

In the liquid detergent of the present invention, the mixing ratio of the component (A) and the component (C) is preferably 30 or less in terms of mass ratio represented by (A) / (C), and is 6 to 15. More preferably, it is more preferably 9-11.
When the mass ratio represented by (A) / (C) is less than or equal to the upper limit value, dyeing of the article to be washed is easily suppressed. On the other hand, when the mass ratio represented by (A) / (C) is less than the lower limit, the coating cleaning power may be reduced.
In the present invention, “mass ratio represented by (A) / (C)” represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent. .

[Solvent: Water]
The liquid detergent of the present invention preferably contains water as a solvent from the viewpoint of ease of preparation of the liquid detergent, solubility in water when used, and the like.
The content of water in the liquid detergent is preferably 15 to 45% by mass, more preferably 25 to 40% by mass with respect to the total mass of the liquid detergent.
If the water content is at least the lower limit, the liquid stability of the liquid detergent with time will be better, and if it is not more than the upper limit, the liquid viscosity will be reasonably low, which is good from the viewpoint of usability. .

[Organic solvent (D)]
The liquid detergent of the present invention preferably further contains an organic solvent (D) represented by the following general formula (d1) (hereinafter also referred to as “component (D)”). By containing the component (D), the coating cleaning power (especially the cleaning power against oil stains and magic stains) is increased, and in addition, dyeing of objects to be washed is further suppressed, especially at low temperatures (assumed in winter). It becomes easy to be done. The component (D) is also effective as a viscosity modifier for the liquid detergent and a gelation inhibitor.

[Wherein R ⁷ represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms; m represents an average number of repetitions of PO; n represents an average number of repetitions of EO; , N is an integer of 0 to 3, and 1 ≦ m + n ≦ 5; EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged. ]

In the formula (d1), R ⁷ is a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. The alkyl group for R ⁷ may be linear or branched.
Specific examples of the linear and branched alkyl groups include CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , and the like. Only one of EO and PO in (EO) n / (PO) m may exist, or they may be mixed and arranged. In (EO) n / (PO) m, EO and PO may be added randomly, or may be added in blocks.

As the component (D), alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol (D1); ethylene glycol, propylene glycol, copolymers of ethylene glycol and propylene glycol, diethylene glycol, triethylene glycol , Alkylene glycol (D2) such as dipropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether Alkylene glycols having 2 to 3 carbon atoms such as Consisting of units of the (poly) alkylene glycol and the alkanol of 1 to 4 carbon atoms (poly) alkylene glycol (mono- or di-) alkyl ether (D3), and the like.

(D) A component may be used individually by 1 type and may use 2 or more types together.
Among these, as the component (D), it is preferable to use at least one organic solvent selected from the group consisting of the above (D1) to (D3), and two or more organic solvents selected from the above group are used. It is more preferable to use a combination of solvents. By using a combination of two or more organic solvents, it is easy to obtain the effects of adjusting the viscosity of the liquid detergent and suppressing gelation.
The content of the component (D) in the liquid detergent is preferably 5 to 20% by mass, more preferably 5 to 18% by mass, and further preferably 5 to 15% by mass with respect to the total mass of the liquid detergent. It is.
When the content of the component (D) is less than the lower limit, it is difficult to obtain an appropriate viscosity, and the liquid cleaning agent is likely to be solidified when applied to an object to be cleaned. On the other hand, when the content of the component (D) exceeds the upper limit value, there is a risk that an odor derived from the component (D) may be generated, and it is not preferable in terms of cost.

[Other ingredients]
In the liquid cleaning agent of the present invention, other components other than the components described above may be blended as necessary within a range not impairing the effects of the present invention.
The other components are not particularly limited, and components usually used in a liquid detergent composition for clothing can be blended, and specific examples include the following components.

The liquid detergent of the present invention may contain alkanolamine for the purpose of improving the appearance stability.
In particular, when an anionic surfactant is blended as the surfactant (A), the alkanolamine is a component that can serve as a counter ion for the anionic surfactant, and the white turbidity that tends to be generated by blending the anionic surfactant It serves to suppress and improve appearance stability. Therefore, in the liquid cleaning agent of the present invention, it is preferable that the surfactant (A) contains an anionic surfactant and further contains an alkanolamine.
As the alkanolamine, an alkanolamine that acts as a counter ion for an anionic surfactant is preferable; an alkanolamine having an alkyl group having 1 to 3 carbon atoms is preferable; an alkanolamine having an alkyl group having 1 to 2 carbon atoms is more preferable. Preferably; monoethanolamine, diethanolamine, and triethanolamine are more preferred.
An alkanolamine may be used individually by 1 type, and may use 2 or more types together.
The content of alkanolamine in the liquid detergent is preferably 0.1 to 3% by mass, more preferably 0.5 to 3% by mass, and still more preferably 0.5% by mass with respect to the total mass of the liquid detergent. ~ 2% by weight.
If content of alkanolamine is 0.1 mass% or more with respect to the total mass of a liquid detergent, the effect which improves the external appearance stability of this composition will be easy to be acquired. Further, when the content of alkanolamine is 3% by mass or less with respect to the total mass of the liquid detergent, the occurrence of the phenomenon that the container is recessed due to oxygen absorption of alkanolamine is easily suppressed.

The liquid detergent of the present invention includes enzymes (proteases, lipases, cellulases, etc.), organic solvents other than component (D), and thickeners (long-chain fatty acid alkylamides) for the purpose of improving washing performance and blending stability. Etc.), texture improvers, pH adjusters, preservatives, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, soil release agents, and the like.
As the pH adjuster, sulfuric acid, sodium hydroxide, potassium hydroxide and the like are preferable from the viewpoint of liquid stability.
Furthermore, a flavoring agent, an emulsifying agent, etc. can also be mix | blended with the liquid cleaning agent of this invention for the purpose of the added value improvement of goods, etc.
As the flavoring agent, the fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A No. 2002-146399 can be used. The content of the flavoring agent is preferably 0.1 to 1% by mass relative to the total mass of the liquid detergent.
Examples of the emulsifying agent include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Specific examples include polystyrene emulsion (manufactured by Seiden Chemical Co., Ltd., “Cybinol RPX-196 PE-3”, solid content 40% by mass). The content of the emulsifying agent is preferably 0.01 to 0.5% by mass relative to the total mass of the liquid detergent.

The pH of the liquid detergent of the present invention is preferably 5 to 10 at 25 ° C., more preferably 5 to 9.5, and still more preferably 5 to 9. The pH is particularly preferably 6-9.
When the pH of the liquid detergent is equal to or higher than the lower limit value, good detergency is easily maintained when the liquid detergent is stored for a long time. When the pH is less than the upper limit value, dyeing of the object to be washed is more easily suppressed. The liquid stability is easily maintained well.
In the present invention, the pH of the liquid detergent (controlled at 25 ° C.) is a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation).

The liquid cleaning agent of the present invention is a liquid cleaning agent that has a high detergency and suppresses dye dyeing to an object to be washed in a concentrated liquid cleaning agent containing a pigment.
In a concentrated liquid cleaning agent containing a pigment, the object to be washed (the object to be cleaned) to which the liquid cleaning agent is applied is left for a while or is rinsed once with a drum-type washing machine or the like. In the case where it is broken (that is, when rinsing is insufficient), there is a problem that the dye tends to be dyed on the object to be washed.
The likelihood of this dyeing on the object to be washed varies depending on the composition of the liquid detergent, the type of clothing (fiber), the temperature, and the water temperature. For example, dyeing is more likely to occur at lower temperature conditions or depending on the type of organic solvent, the more hydrophobic fibers (such as polyester fibers).
The reason why pigments are dyed on the object to be washed is that the high concentration surfactant and the object to be washed are in contact with each other for a long time, or the surfactant is partially applied to the object to be washed due to insufficient rinsing. The surfactant may permeate the clothing (fiber) too much, and the pigment will be adsorbed deeply into the clothing (fiber). It is possible that
Further, depending on the temperature condition and the standing time, moisture and solvent in the liquid detergent evaporate and the composition gels, so that the liquid detergent cannot be sufficiently dissolved in water at the time of washing. For this reason, it can be considered that the dye is easily dyed on the object to be cleaned by bringing the high concentration surfactant into contact with the object to be cleaned for a long time.
In the liquid cleaning agent of the present invention, urea or a derivative thereof (C) is contained together with 40% by mass or more of the surfactant with respect to the total mass of the liquid cleaning agent and the dye. While component (C) is a highly hydrophilic substance, its interaction with the surfactant is strong due to its structural characteristics, so component (C) is around the surfactant molecule in the formulation. It is thought that it exists easily. Thereby, at the time of application | coating washing | cleaning, adsorption | suction and osmosis | permeation to the clothing of surfactant are suppressed by presence of (C) component, and interaction with a hydrophobic fiber and surfactant is also suppressed. As a result, it is estimated that the effects of the present invention can be obtained.
According to the liquid cleaning agent of the present invention, even when the object to be cleaned to which the liquid cleaner is applied is left for a while or the rinsing is insufficient, dyeing of the object to be cleaned is suppressed.

In addition, according to the liquid detergent of the present invention, by containing the component (C), in particular, an anionic surfactant that suppresses recontamination, and an alkanolamine that can be a counter ion of the anionic surfactant, The yellowing of the liquid color, which is likely to occur when using together, is also suppressed, and the appearance stability is kept good.
The liquid cleaning agent of the present invention exhibits a high cleaning effect with a small amount of cleaning agent used.
The liquid detergent of the present invention is particularly suitable for clothing, and is a liquid detergent that contains a pigment and is suitable for a composition having a high surfactant concentration (concentrated composition).

As one aspect of the liquid cleaning agent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), and an organic solvent (D), with respect to the total mass of the liquid detergent,
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis),
Examples thereof include liquid detergents in which the component (C) is 0.5 to 12% by mass, the component (D) is 5 to 20% by mass, and the total amount of the components does not exceed 100% by mass.

As other aspects of the liquid detergent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), and water, with respect to the total mass of the liquid detergent,
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis), the component (C) is 0.5 to 12% by mass, the water is 15 to 45% by mass, and the total amount of the components is 100% by mass. % Liquid detergents not exceeding%.

As other aspects of the liquid detergent of the present invention,
A liquid detergent containing a surfactant (A), a dye (B), urea or a derivative thereof (C), an organic solvent (D), and water, wherein the total mass of the liquid detergent Whereas
The component (A) is 40 to 70% by mass,
The component (B) is 1 to 150 ppm (mass basis),
The component (C) is 0.5 to 12% by mass,
Examples thereof include liquid detergents in which the component (D) is 5 to 20% by mass, the water is 15 to 45% by mass, and the total amount of each component does not exceed 100% by mass.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

The compositions of the liquid detergents in each example are shown in Tables 1 to 3.
The raw materials used in this example are as follows.

[Surfactant (A)]
A-1: C ₁₁ H ₂₃ CO— (OC ₂ H ₄ ) ₁₅ —OCH ₃ , narrow ratio 33% by mass; synthetic product. A-1 was produced by a method based on the method described in JP-A-2002-144179. That is, alumina hydroxide / magnesium hydroxide (trade name Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) having a chemical composition of 2.5 MgO.Al ₂ O ₃ .nH ₂ O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere. 4 g of calcined alumina hydroxide / magnesium catalyst (unmodified) obtained as described above, 2.9 mL of 0.5N potassium hydroxide ethanol solution as a surface modifier, and 350 g of lauric acid methyl ester A liter autoclave was charged, and the catalyst was reformed in the autoclave. Next, after replacing the inside of the autoclave with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure of 3 × 10 5 Pa, 1079 g of ethylene oxide was introduced and reacted while stirring.
Next, the reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth were added as filter aids, respectively, and the catalyst was filtered to obtain A-1 as the target product.

A-2: Mixture of C ₁₁ H ₂₃ CO— (OC ₂ H ₄ ) ₁₅ —OCH ₃ and C ₁₃ H ₂₇ CO— (OC ₂ H ₄ ) ₁₅ —OCH ₃ in a mass ratio of 8/2, narrow ratio 33% by mass; synthetic product.
However, A-2 was synthesized in the same manner as A-1, except that instead of 350 g of lauric acid methyl ester, a mixture of 280 g of lauric acid methyl ester and 70 g of myristic acid was used and 1052 g of ethylene oxide was introduced. Manufactured with.

A-3: A 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 added in block order to a primary alcohol having 10 to 14 carbon atoms. R ⁶ in the general formula (a3) = a linear alkyl group having 10 to 14 carbon atoms, p = 9, q = 2, r = 9.

A-4: Nonionic surfactant obtained by adding an average of 9 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms, trade name Softanol 90, manufactured by Nippon Shokubai Co., Ltd. R ⁴ in the general formula (a2) = branched alkyl group having 12 to 14 carbon atoms, t = 9.

A-5: Polyoxyethylene alkyl (C12-13) ether. Raw material alcohol Saffol 23 (product name, manufactured by Sasol Co., Ltd .: C12 / C13 = 55% / 45% mixture by mass ratio of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms, linear chain with respect to the entire carbon chain The average carbon chain ratio is 50% by mass) and an average of 15 moles of ethylene oxide is added.

A-6: linear alkyl (carbon number 10 to 14) benzenesulfonic acid [manufactured by Lion Corporation, trade name Rypon LH-200 (LAS-H pure content 96 mass%)].
A-7: AES-Na, sodium polyoxyethylene alkyl ether sulfate having 12 to 13 carbon atoms (average addition mole number of ethylene oxide 2), synthetic product (raw alcohol is trade name Neodol 23, manufactured by Shell).

A-8: Natural alcohol (trade name CO-1214 manufactured by P & G) with 12 mole equivalent of ethylene oxide added [LMAO (C12 / 14-15EO)], synthetic product. The synthesis was performed as follows.
861.2 g of a trade name “CO-1214” manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. Next, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, it added, adjusting the addition rate so that reaction temperature might not exceed 180 degreeC using the blowing tube. After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, 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 lower, 70% by mass p-toluenesulfonic acid was added to neutralize so that the pH of the 1% by mass aqueous solution of the reaction product was about 7, and LMAO (C12 / 14 -15EO).

[Dye (B)]
B-1: C.I. I. Food Green 3, Green No. 3, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelength 610 nm.
B-2: Liquid Blue Blue, manufactured by Milliken Co .; maximum absorption wavelengths of 595 nm and 645 nm.
B-3: C.I. I. Solvent Blue 63, Blue No. 403, manufactured by Sakai Kasei Co., Ltd .; maximum absorption wavelengths of 600 nm and 645 nm.

[Urea (C)]
C-1: Urea, reagent, manufactured by Junsei Chemical Co., Ltd.
C-2: 1,3-dimethylurea, reagent, manufactured by Tokyo Chemical Industry Co., Ltd.

[Organic solvent (D) represented by general formula (d1)]
D-1: 1,2-propanediol (trade name: propylene glycol, manufactured by Showa Denko KK) 100% by mass pure. R ⁷ in formula (d1) = hydroxy group, m = 1, n = 0.
D-2: Butyl carbitol (trade name butyl diglycol, manufactured by Nippon Emulsifier Co., Ltd.) 100% by mass pure. R ⁷ in the general formula (d1) = ethyl group, m = 0, n = 3.
D-3: Ethanol (trade name: specified alcohol 95 degree synthetic alcohol, manufactured by Nippon Alcohol Sales Co., Ltd.) In the general formula (d1), R ⁷ = hydrogen atom, m = 0, n = 1.

[Other ingredients]
MEA: Monoethanolamine (manufactured by Nippon Shokubai Co., Ltd.) 100% by mass pure.
DEA: 100% by mass of diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
Polyethylene glycol: manufactured by Lion Chemical Co., Ltd., trade name “PEG # 1000-L60”, polymerization degree 20.
Enzyme: Protease, trade name “Everlase 16L TYPE EX”, manufactured by Novozymes.
Citric acid: manufactured by Fuso Chemical Industries, Ltd., 100% pure content.
pH adjuster: KOH (Asahi Glass Co., Ltd.) and sulfuric acid (Toho Zinc Co., Ltd.).
Ion exchange water.

<Example of manufacturing liquid detergent>
According to the blending components and contents (mass%) of the compositions shown in Tables 1 to 3, liquid detergents of each example were produced by the following production methods (when there are blank blending components in the table, the blending components are Not blended).
In the table, the content of the compounding component indicates a pure equivalent amount. In addition, only content of (B) component is displayed by "ppm" (mass basis).
The “balance” indicating the water content indicates a blending amount adjusted so that the total amount of the liquid cleaning agent as the final preparation is 100% by mass.
The “appropriate amount” indicating the content of the pH adjusting agent indicates an amount blended for adjusting the pH (25 ° C.) of the liquid cleaning agent to the pH shown in the table.
“Mass ratio: (A) / (C)” represents the ratio (mass ratio) of the content of component (A) to the content of component (C) in the liquid detergent.

(Examples 1 to 19, Comparative Examples 1 to 3, Reference Example 1)
In a 500 mL beaker, the component (D) of the content (mass%) shown in the table, polyethylene glycol, MEA or DEA, and A-6 or A-7 were added and stirred (in the table, If there is a blank compounding component, the compounding component is not blended). Subsequently, (C) component aqueous solution (concentration 50 mass%) and citric acid aqueous solution (concentration 50 mass%) which respectively dissolved (C) component and citric acid in water were added and stirred.
Subsequently, it adjusted so that pH (25 degreeC) of a solution might become the value shown in a table | surface using the pH adjuster.
Next, the remaining component (A) was added and stirred. Next, the enzyme was added and stirred, and then, an aqueous dye solution (dye concentration 1000 ppm) in which the component (B) was dissolved in water was added and stirred to a predetermined concentration. Thereafter, ion-exchanged water was added so that the total amount of the final preparation was 100% by mass, thereby obtaining each of the liquid cleaning agents in each example.
The pH of the solution (25 ° C.) was measured by adding the pH meter electrode to the solution adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) It was measured by reading the value.

<Evaluation of liquid detergent>
With respect to the liquid cleaning agents of the respective examples, “application cleaning power”, “dyeing property to clothes”, and “appearance stability” were evaluated by the following evaluation methods. The results are also shown in Tables 1 to 3.

[Coating cleaning power]
Contaminated cloth preparation:
Five cotton knitted fabrics (5cm x 5cm) were applied in black with a circular shape (diameter 2cm) so that the ink was evenly distributed with oil-based magic (magic ink / Gokuhoso M700-T1). A contaminated cloth for detergency evaluation was used.

(Cleaning conditions)
After applying a standard amount of liquid detergent (concentrated type 10g / water 30L, normal type 20g / water 30mL) to 30L of water on each of the 5 contaminated cloths, the liquid detergent was left at a temperature of 20 ° C for 5 minutes. . Specifically, the application amount of the liquid cleaning agent per contaminated cloth is 0.3 g for each of Examples 1 to 19 and Comparative Examples 1 to 3 (concentrated type), and 0.6 g for Reference Example 1. It was.
After that, in Terg-o-meter (UNITED STATES TESTING), 15 mL of 3 ° DH hard water 900 mL, 5 sheets of contaminated cloth and skin shirt (LL size, DVD) are finely (about 3 cm x 3 cm) What was cut was put into a bath ratio of 20 times and washed at 120 rpm and 15 ° C. for 10 minutes.
(Rinsing conditions)
After the washing, it was dehydrated for 1 minute, and then rinsed with 900 mL of 15 ° C. 3 ° DH hard water at 120 rpm and 15 ° C. for 3 minutes. This dehydration and rinsing was repeated twice.
(Drying conditions)
After the second rinsing, it was dehydrated for 1 minute, and after washing, the soiled cloth was sandwiched between filter papers one by one and dried with an iron.

The coating cleaning power was evaluated by measuring the reflectance (Z value) using a reflectance meter (spectral color difference meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.) before and after cleaning. %).
Washing rate (%) = (Z value of contaminated cloth after washing−Z value of contaminated cloth before washing) / (Z value of raw cloth−Z value of contaminated cloth before washing) × 100
In the formula, “raw fabric” refers to cotton knitted fabric that has not been subjected to contamination treatment in the preparation of the above-mentioned contaminated fabric.
For each example, the cleaning rate (%) of 5 contaminated cloths was calculated, the average value thereof was determined, and the coating cleaning power was evaluated based on the following evaluation criteria. ◎, ○, and △ were considered acceptable.
Evaluation criteria A: The average value of the cleaning rate (%) was 15% or more.
A: The average value of the cleaning rate (%) was 10% or more and less than 15%.
Δ: The average value of the cleaning rate (%) was 5% or more and less than 10%.
X: The average value of the cleaning rate (%) was less than 5%.

[Evaluation of dyeing property to clothing]
Only a longitudinal end portion (thickened portion, seam allowance portion) of a white hand-wiped cotton towel (29 cm × 72 cm) was cut out and used as an evaluation sample (cotton) (5 g by mass).
Next, 5 g of the liquid detergent for standard usage (15 g) for 4 kg of laundry was applied to the evaluation sample (cotton) and left for 12 hours.
Thereafter, the sample for evaluation (cotton) coated with 5 g of detergent and a cotton skin shirt as a charge cloth were put together in a washing machine so as to be 4 kg, and the remaining liquid detergent was added for washing.
The washing conditions at that time were set as follows. A Toshiba drum type washing machine (product name TW-4000VFL) was used as the washing machine. The washing course was set at a washing time of 10 minutes, designated once for rinsing and dehydration for 8 minutes.
The above operations (in the case of cotton towels) were performed under the conditions of summer and winter.
Assuming summertime, an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 25 ° C. for 12 hours, and water adjusted to 25 ° C. during washing was used.
Assuming winter season, an evaluation sample (cotton) coated with 5 g of a liquid detergent was left at a temperature of 5 ° C. for 12 hours, and water adjusted to 5 ° C. during washing was used.

Further, a polyester (PE) jersey (Tanigami Shoten) was cut into 5 cm × 5 cm, and used as a sample for evaluation (PE) (0.2 g by mass).
Next, 2 g of the standard amount (15 g) of liquid detergent used for 4 kg of laundry was applied to the evaluation sample (PE) and allowed to stand for 12 hours.
Thereafter, the sample for evaluation (PE) coated with 5 g of detergent and a cotton skin shirt as a charge cloth are put into a washing machine so as to be 4 kg in total, and the remaining liquid detergent is added, and the same as the above washing conditions. Laundry was performed under conditions.
The above operation (in the case of PE) was performed only under the same summer conditions as described above.

Then, whether or not dyeing was observed on the evaluation sample (cotton) after washing and the evaluation sample (PE) was visually determined and evaluated based on the following evaluation criteria. ◎, ○, and △ were considered acceptable.
Evaluation criteria (double-circle): Dyeing | dye dyeing was not recognized at all in the sample for evaluation after washing.
○: Slight dyeing was observed in the evaluation sample after washing.
Δ: Some dyeing was observed in the evaluation sample after washing.
X: Dyeing was clearly recognized in the sample for evaluation after washing.

[Appearance stability]
Immediately after production, 100 g of the liquid detergent of each example was placed in a cylindrical glass bottle (PS100), sealed with a lid, and stored at 50 ° C. for 30 days.
And the change of the external appearance (liquid color) of the liquid detergent after storage was judged visually, and it evaluated based on the following evaluation criteria. ◎ and ○ were accepted.
In addition, when the liquid detergent is yellowed by storage, the blue color before storage (initial) is changed to green, and the green color is initially changed to yellow-green.
Evaluation Criteria A: No change in appearance (liquid color) was observed compared to the initial value.
○: It was recognized that the blue color at the initial stage changed to green, and the green color at the initial stage changed to yellowish green.
X: It was clearly recognized that the initial blue color changed to green, and the initial green color changed to yellow-green.

From the results shown in Tables 1 to 3, it was confirmed that the liquid detergents of Examples 1 to 19 had high detergency and suppressed dyeing to the object to be washed.

The present invention is extremely industrially useful because it can provide a liquid cleaning agent that has a high detergency and suppresses dye dyeing to an object to be washed in a concentrated liquid cleaning agent containing a pigment.

Claims

Liquid detergent containing 40% by mass or more of surfactant (A), 150 ppm (mass basis) or less of dye (B), and 0.5 to 12% by mass of urea or its derivative (C).
The liquid cleaning according to claim 1, wherein the surfactant (A) comprises at least one surfactant selected from nonionic surfactants represented by the following general formulas (a1) to (a3): Agent.

[In the formula (a1), R 1 is a linear or branched alkyl group or alkenyl group having 5 to 21 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, and R 3 is carbon An alkyl group having a number of 1 to 4, s represents an average number of repetitions of OR 2 and a number of 5 to 30; in formula (a2), R 4 is a hydrocarbon group having 10 to 22 carbon atoms; R 5 represents an alkylene group having 2 to 4 carbon atoms, t represents an average number of repeating R 5 O, and is a number of 5 to 20; in formula (a3), R 6 represents an alkyl having 10 to 16 carbon atoms A group or an alkenyl group, p represents the average number of repetitions of EO, q represents the average number of repetitions of PO, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0 , 0 <q ≦ 3, and p + r = 10-30, EO represents an oxyethylene group, PO represents oxy It represents a propylene group, or may be arranged in a mixed manner and EO and PO in (EO) p / (PO) q. ]
The liquid cleaning agent of Claim 1 or Claim 2 which further contains the organic solvent (D) represented by the following general formula (d1).

[Wherein R 7 represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms; m represents an average repeat number of PO, n represents an average repeat number of EO, and m represents 0 to 2 N is an integer of 0 to 3, and 1 ≦ m + n ≦ 5, EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO may be mixed and arranged Good. ]