JP5789394B2 - Liquid cleaning agent - Google Patents

Description

  The present invention relates to a liquid detergent containing urea.

Recently, as a detergent used for washing at home, it has features different from powder detergents (no undissolved residue, you can enjoy aroma, etc.) and it is affordable, so the demand for liquid detergents is increasing. .
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.

A liquid detergent having a high content of surfactant has a problem that, with time, the liquid detergent itself tends to gel, particularly on the liquid surface, resulting in poor usability. If the liquid cleaning agent is gelled, it becomes difficult to measure (measure) the liquid cleaning agent into the cap, 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).

Further, when measuring the liquid cleaning agent into the cap, in the case of a liquid having a colorless and transparent appearance, it is difficult to collate with the scale of the cap, so that the amount measured to the cap is likely to be more or less than a 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 the case of 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, the liquid cleaning agent of the present invention comprises 40% by mass or more of the surfactant (A), 150 ppm (mass basis) or less of the dye (B), 0.5 to 12% by mass of urea or its derivative (C). And 50% by mass or more of the surfactant (A) is at least one selected from nonionic surfactants represented by any one of the following general formulas (a1) to (a3): (a) / (C) weight ratio expressed by is characterized der Rukoto 30 below.

［式（ａ１）中、Ｒ^１は炭素数５〜２１の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜４のアルキル基である。ｓはＯＲ^２の平均繰返し数を示し、５〜３０の数である。式（ａ２）中、Ｒ^４は炭素数１０〜２２の炭化水素基であり、Ｒ^５は炭素数２〜４のアルキレン基である。ｔはＲ^５Ｏの平均繰返し数を示し、５〜２０の数である。式（ａ３）中、Ｒ^６は炭素数１０〜１６のアルキル基又はアルケニル基である。ｐはＥＯの平均繰返し数を表し、ｑはＰＯの平均繰返し数を表し、ｒはＥＯの平均繰返し数を表し、ｐ、ｑ、ｒはｐ＞１、ｒ≧０、０＜ｑ≦３、ｐ＋ｒ＝１０〜３０を満たす数である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、（ＥＯ）ｐ／（ＰＯ）ｑにおけるＥＯとＰＯとは混在して配列してもよい。］

[In 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. It is a C 1-4 alkyl group. s represents an average repeating number of OR ^2, a number of 5 to 30. In formula (a2), R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, and R ⁵ is an alkylene group having 2 to 4 carbon atoms. t represents an average repeating number of ^{R 5} O, the number of 5-20. In the formula (a3), R ⁶ is 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, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0, 0 <q ≦ 3, p + r = 10-30. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) p / (PO) q may be mixed and arranged. ]

In the liquid cleaning agent of the present invention, it is preferable that the surfactant (A) further contains an anionic surfactant.
Moreover, in the liquid cleaning agent of this invention, it is preferable to further contain the organic solvent (D) represented by the following general formula (d1).

［式中、Ｒ^７は水素原子、ヒドロキシ基、又は炭素数１〜４のアルキル基である。ｍはＰＯの平均繰返し数、ｎはＥＯの平均繰返し数を表し、ｍは０〜２の数、ｎは０〜３の数であり、１≦ｍ＋ｎ≦５である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein, R ⁷ represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. m represents the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 2, n is a number 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. ]

  ADVANTAGE OF THE INVENTION According to this invention, in the concentration type liquid cleaning agent containing a pigment | dye, while having high detergency, the liquid cleaning agent by which the pigment | dye dyeing to to-be-washed | cleaned material was suppressed can be provided.

The liquid detergent of the present invention contains 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). To do.
Hereinafter, these three components are also referred to as component (A), component (B), and component (C), respectively.

[Surfactant (A)]
As the surfactant (A), those generally used for liquid detergents for clothing such as nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants can be blended.

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

［式（ａ１）中、Ｒ^１は炭素数５〜２１の直鎖状もしくは分岐鎖状のアルキル基又はアルケニル基であり、Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３は炭素数１〜４のアルキル基である。ｓはＯＲ^２の平均繰返し数を示し、５〜３０の数である。］

[In 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. It is a C 1-4 alkyl group. s represents an average repeating number of OR ^2, a number 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.
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 repeating number of OR ^2, a number 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. The narrow ratio is more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass. The higher the narrow ratio, the better the detergency can be obtained. However, if it is too high, the stability over time 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). Can be easily manufactured by the method described in Japanese Unexamined Patent Publication No. 2000-144179.
Specific examples of such a surface-modified composite metal oxide catalyst include metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co 1) that have been surface-modified with a metal hydroxide or the like. ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) and a composite metal oxide catalyst such as magnesium oxide, or a hydrotalcite calcined catalyst whose surface is modified with a metal hydroxide and / or metal alkoxide, etc. Etc.
Further, in the surface modification of the composite metal oxide catalyst, the mixing ratio of the composite metal oxide and the metal hydroxide and / or metal alkoxide is changed to metal hydroxide with respect to 100 parts by mass of the composite metal oxide. The ratio of the product and / or metal alkoxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass.

［式（ａ２）中、Ｒ^４は炭素数１０〜２２の炭化水素基であり、Ｒ^５は炭素数２〜４のアルキレン基である。ｔはＲ^５Ｏの平均繰返し数を示し、５〜２０の数である。］

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

In the formula (a2), the carbon number of ^{R 4} is 10 to 22, preferably 10 to 20, more preferably 10 to 18. The hydrocarbon group for R ⁴ may be linear or branched, and may have an unsaturated bond. The component represented by the formula (a2) may be composed of a single chain length or a mixture 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 coconut oil, palm oil and beef tallow, and synthetic alcohols derived from petroleum 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.

Formula (a2) in, t represents an average repeating number of ^{R 5} O, the number of 5 to 20, preferably a number number of 8 to 18, more preferably 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, a relatively wide distribution is obtained. Alkylene oxide is added to the hydrophobic group raw material using a specific alkoxylation catalyst such as magnesium oxide to which metal ions such as ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ²⁺ are added. Tend to have a relatively narrow distribution.

  Specific examples of the component represented by the formula (a2) include a trade name Neodol manufactured by Shell (mixture of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms: C12 / C13), Safol23 manufactured by Sasol (C12 / C13) or the like with 12 or 15 moles of ethylene oxide added to an alcohol; P & G's product names CO-1214 or CO-1270 or other natural alcohols with 9, 12 or 15 moles of ethylene oxide Those added: those obtained by adding 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).

［式（ａ３）中、Ｒ^６は炭素数１０〜１６のアルキル基又はアルケニル基である。ｐはＥＯの平均繰返し数を表し、ｑはＰＯの平均繰返し数を表し、ｒはＥＯの平均繰返し数を表し、ｐ、ｑ、ｒはｐ＞１、ｒ≧０、０＜ｑ≦３、ｐ＋ｒ＝１０〜３０を満たす数である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、（ＥＯ）ｐ／（ＰＯ）ｑにおけるＥＯとＰＯとは混在して配列してもよい。］

[In 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, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0, 0 <q ≦ 3, p + r = 10-30. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) p / (PO) q may be mixed and arranged. ]

The formula (a3), the alkyl group in ^{R 6,} carbon atoms in the alkenyl group is 10 to 16, is preferably 10 to 14. The alkyl group and alkenyl group for R ⁶ may be linear or branched.
In the formula (a3), r is r ≧ 0, preferably r ≧ 1. p + r = 10-30, preferably p + r = 14-20.
In the formula (a3), the ratio of EO and PO is preferably 0.1 to 0.5, more preferably 0.1 to 0.3, as a ratio represented by q / (p + r). 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 it is at most 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. For example, it can be synthesized by adding ethylene oxide and propylene oxide in this order to alcohol derived from natural fats or oils, or after adding and mixing ethylene oxide and propylene oxide (random addition), and then adding ethylene oxide again. .

The polyoxyalkylene alkyl ether is a polyoxyalkylene obtained by adding an average of 3 to 30 mol, preferably 5 to 20 mol, of an alkylene oxide having 2 to 4 carbon atoms to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Examples thereof include alkylene alkyl ethers and polyoxyalkylene alkenyl ethers (alcohol alkoxylates). 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.
Specifically, the anionic surfactant has a linear alkylbenzene sulfonate (LAS) having an alkyl group having 8 to 16 carbon atoms (preferably 10 to 14 carbon atoms) and an alkyl group having 10 to 20 carbon atoms. Alkyl sulfate (AS), poly (alkylene) 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) Grade alkane sulfonate (SAS), α-sulfo fatty acid methyl ester salt having an alkyl group having 10 to 20 carbon atoms (α-SF), 10 to 10 carbon atoms 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.

  Polyoxyethylene alkyl ether sulfate is ethylene oxide when the number of moles of ethylene oxide adduct of the ethylene oxide adduct most present on a mass basis in the total ethylene oxide adduct constituting the polyoxyethylene alkyl ether sulfate is “nlmax”. The total proportion of the ethylene oxide adducts of (nlmax-1), nlmax, and (nlmax + 1) is preferably 55% by mass or more based on the total ethylene oxide adduct, and is in the range of 55 to 80% by mass. Is more preferable. Within this range, the fluidity of the polyoxyethylene alkyl ether sulfate is increased and the manufacturability is improved.

  Among these, as anionic surfactants, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates and secondary alkane sulfonates are preferred because of their good anti-recontamination properties, and alkylbenzene sulfonates. Polyoxyethylene alkyl ether sulfates are more preferable, and alkylbenzene sulfonates are particularly preferable.

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. .
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 or in combination of 2 or more types.
Among the above, as the component (A), it is preferable to use a nonionic surfactant or an anionic surfactant.
In particular, the component (A) preferably contains 50% by mass or more of nonionic surfactant, more preferably contains 80% by mass or more of nonionic surfactant, and 90% by mass of nonionic surfactant. % Or more is preferable, 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 preferably includes at least one selected from nonionic surfactants represented by the general formulas (a1) to (a3) because of its high detergency.
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.

Content of (A) component in a liquid cleaning agent is 40 mass% or more with respect to the total mass of a liquid cleaning agent, it is preferable that it is 40-70 mass%, and it is 45-65 mass%. More preferred.
When the content of the component (A) is 40% by mass or more, 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, gelation of the liquid detergent on the liquid surface is difficult to occur with time, and the liquid surface A film is hardly formed.

When using an anionic surfactant together 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, on the liquid surface of the liquid cleaning agent, the liquid cleaning agent itself is difficult to gel and a film is hardly formed. Further, the coating cleaning power is improved satisfactorily. When the content of the anionic surfactant is 1% by mass or more, 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, Examples include oxidation dyes. The structure of each dye is described in the “Legal Handbook” (edited by Japan Cosmetic Industry Association).
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.
Among the above, Solvent dyes (oil-soluble) dyes are chemically modified with water-soluble polymers such as polyethylene glycol and 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.

As the component (B), one type may be used alone, or two or more types may be used in combination.
Among these, as the component (B), since the effect of the present invention is remarkably easily exhibited, 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. A blue to green dye having a maximum absorption wavelength at 590 to 650 nm is particularly preferable.
The content of the component (B) in the liquid cleaning agent is 150 ppm (mass basis) or less (0.015 mass) with respect to the total mass of the liquid cleaning agent, based on the dyeing property to the object to be cleaned and the liquid color degree by blending. 1 to 100 ppm (mass basis) (0.0001 to 0.01 mass%) is preferred, and 3 to 50 ppm (mass basis) (0.0003 to 0.005 mass%) is more preferred.
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, if the upper limit is exceeded, dyeing of 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.
Urea double salts 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 · (5-6) 4CO (NH ₂ ) ₂ · 2H ₂ O or the like can be used.

  In the present invention, “urea derivatives” include those having a structure represented by the following general formula (c1). Among the urea derivatives, the compound represented by the general formula (c1-1) is preferably exemplified.

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 and N- (2-hydroxyethyl) urea.

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 value, dyeing of the object to be washed may not be sufficiently suppressed. On the other hand, when the upper limit value is exceeded, ammonia is likely to be generated as a decomposition product after storage. 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. Is more preferable, and it is more preferable that it is 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, if it 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.
15-45 mass% is preferable with respect to the total mass of a liquid cleaning agent, and, as for content of the water in a liquid cleaning agent, 25-40 mass% is more preferable.
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 and a gelation inhibitor for the liquid detergent.

［式中、Ｒ^７は水素原子、ヒドロキシ基、又は炭素数１〜４のアルキル基である。ｍはＰＯの平均繰返し数、ｎはＥＯの平均繰返し数を表し、ｍは０〜２の数、ｎは０〜３の数であり、１≦ｍ＋ｎ≦５である。ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基を表し、ＥＯとＰＯとは混在して配列してもよい。］

[Wherein, R ⁷ represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms. m represents the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 2, n is a number 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 formula (d1), ^{R 7} is a hydrogen atom, hydroxy group, or an alkyl group having 1 to 4 carbon atoms. The alkyl group for R ⁷ may be linear or branched.
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.

  (D) Component includes alkanols such as ethanol, 1-propanol, 2-propanol, 1-butanol (D1); ethylene glycol, propylene glycol, copolymer 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 C2-C3 alkylene grease such as Consisting of Lumpur unit (poly) alkylene glycol and the alkanol of 1 to 4 carbon atoms (poly) alkylene glycol (mono- or di-) alkyl ether (D3), and the like.

As the component (D), one type may be used alone, or two or more types may be used in combination.
Among these, as the component (D), it is preferable to use at least one selected from the group consisting of the above (D1) to (D3), and a combination of two or more selected from the group is used. Is more preferable. By using two or more types in combination, it becomes 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 upper limit is exceeded, 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.
Other components are not particularly limited, and components usually used in liquid detergent compositions for clothing can be blended, and specific examples include the following.

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 be a counter ion of the anionic surfactant, and the cloudiness or the like that is likely to occur due to the blending of 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.
The alkanolamine is preferably one that acts as a counter ion of an anionic surfactant, preferably an alkanolamine having an alkyl group having 1 to 3 carbon atoms, and more preferably an alkanolamine having an alkyl group having 1 to 2 carbon atoms. Monoethanolamine, diethanolamine, and triethanolamine are more preferable.
An alkanolamine may be used alone or in combination of two or more.
The content of the alkanolamine in the liquid detergent is preferably from 0.1 to 3% by mass, more preferably from 0.5 to 3% by mass, and still more preferably from 0.5 to 3% by mass with respect to the total mass of the liquid detergent. It is -2 mass%.
If content of alkanolamine is 0.1 mass% or more, the effect which improves the external appearance stability of this composition will be easy to be acquired. Moreover, if content of alkanolamine is 3 mass% or less, generation | occurrence | production of the phenomenon that a container dents by oxygen absorption of alkanolamine is easy to be 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 a flavoring agent, the fragrance compositions A, B, C, D and the like described in Tables 11 to 18 of JP-A-2002-146399 can be used. The content of the flavoring agent is preferably 0.1 to 1% by mass with respect 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 suitably used. Specific examples include polystyrene emulsion (Saiden 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 with respect 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, dyeing of the article 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.) indicates a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) or the like.

The liquid cleaning agent of the present invention is a concentrated liquid cleaning agent containing a pigment, which has a high detergency and suppresses dye dyeing to an object to be washed.
In a concentrated type liquid detergent containing a pigment, the object to be washed (the object to be washed) to which the liquid detergent is applied is left for a while or is rinsed once with a drum-type washing machine or the like. When it is broken (when rinsing is insufficient), there is a problem that the dye is likely 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 this invention, urea and its derivative (C) are contained with 40 mass% or more of surfactants and a pigment | 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.

Further, 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 contains a pigment and is suitable for a composition having a high surfactant concentration (concentrated composition).

  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 composition of the liquid cleaning agent in each example is shown in Tables 1-3.
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 wt%; synthetic. A-1 was manufactured by the method based on the method as described in Unexamined-Japanese-Patent No. 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 as filter aids were added, respectively, and the catalyst was filtered to obtain A-1 as the target product.

A-2: 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 in 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: 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 block-added to a primary alcohol having 10 to 14 carbon atoms in order. 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: A product 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 .: a mixture of C12 / C13 = 55% / 45% by mass ratio of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms, linear to the total 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 (C10-C14) benzenesulfonic acid [manufactured by Lion Corporation, trade name Rypon LH-200 (LAS-H pure content: 96% by mass)].
A-7: AES-Na, C12-13 polyoxyethylene alkyl ether sodium sulfate (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 mol 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 Co. and 2.0 g of a 30% by mass NaOH aqueous solution were collected in 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 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 Corporation; maximum absorption wavelengths 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. 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”, degree of polymerization 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). However, Example 14 is a reference example.
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 1-19, Comparative Examples 1-3, Reference Example 1)
In a 500 mL beaker, the component (D) having a content (mass%) shown in the table, polyethylene glycol, MEA or DEA, and either A-6 or A-7 were added and stirred. 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 adjusted to a temperature adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation), and the pH meter electrode was added after 2 minutes. 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 1-3.

[Coating cleaning power]
Contaminated cloth preparation:
Five cotton knitted fabrics (5cm x 5cm) were applied to each example in 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 coating amount of the liquid detergent per one piece of 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, on Terg-o-meter (UNITED STATES TESTING), 900 mL of 15 ° C. 3 ° DH hard water, 5 sheets of contaminated cloth and skin shirt (LL size, manufactured by DVD) are finely (about 3 cm × 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 in a washing machine so as to be 4 kg in total, 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 in 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 of Tables 1 to 3, it was confirmed that the liquid detergents of Examples 1 to 19 had high detergency and that dye dyeing to the article to be washed was suppressed.

Claims (3)

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) ,
50% by mass or more of the surfactant (A) is at least one selected from nonionic surfactants represented by any one of the following general formulas (a1) to (a3),
(A) / Der Ru liquid detergent mass ratio of 30 or less represented by (C).

[In 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. It is a C 1-4 alkyl group. s represents an average repeating number of OR ^2, a number of 5 to 30. In formula (a2), R ⁴ is a hydrocarbon group having 10 to 22 carbon atoms, and R ⁵ is an alkylene group having 2 to 4 carbon atoms. t represents an average repeating number of ^{R 5} O, the number of 5-20. In the formula (a3), R ⁶ is 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, r represents the average number of repetitions of EO, p, q, r are p> 1, r ≧ 0, 0 <q ≦ 3, p + r = 10-30. EO represents an oxyethylene group, PO represents an oxypropylene group, and EO and PO in (EO) p / (PO) q may be mixed and arranged. ] The liquid detergent according to claim 1, wherein the surfactant (A) further comprises an anionic surfactant . 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 the average number of repetitions of PO, n represents the average number of repetitions of EO, m is a number of 0 to 2, n is a number 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. ]