JP2015074762A - Flowable detergent and container-packed detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flowable detergent combining the advantage of a powder detergent capable of holding solid granules uniformly and the advantage of a liquid detergent having measurability in use, solubility in washing liquid, etc.SOLUTION: A flowable detergent has a thixotropy index of 5-2. The detergent typically comprises (A) a specified nonionic surfactant of formula (1), (B) one or more selected from polyethylene glycol of a mass average molecular weight of 9,000-200,000 and methoxy-polyethylene glycol, (C) one or more selected from alkali agents and inorganic builders and (D) water, each in a specified content. In formula (1), R is a 9-17C alkyl or alkenyl group; and n, an average repeating number of oxyethylene groups, is 10-20.

Description

  The present invention relates to a fluid detergent and a container detergent suitable for washing clothes.

Conventionally, powder detergents and liquid detergents have been widely used as detergents for washing clothes. The powder cleaning agent contains an inorganic builder, an alkali agent, and the like in addition to the surfactant, thereby exhibiting excellent cleaning power against various types of dirt. On the other hand, the liquid detergent contains a large amount of nonionic surfactant and exhibits a high detergency especially against sebum soil. Among these, the demand for liquid detergents is increasing for reasons such as easy weighing during washing and excellent solubility in washing liquids.
In recent years, it has been demanded to reduce the amount of detergent required for one washing because of changes in washing circumstances and increased awareness of environmental load.

  Against this background, so-called “concentrated type” liquid detergents have been developed that contain a high concentration of surfactant and exhibit a high cleaning effect with a small amount of detergent used. For example, Patent Document 1 proposes a liquid detergent containing a surfactant composed of a specific ethylene oxide adduct in a high concentration. Such an ethylene oxide adduct is obtained by, for example, addition polymerization of ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst as described in Patent Document 2, for example.

JP 2009-007451 A JP 2000-144179 A

  However, as described above, the liquid detergent exhibits a high detergency against sebum dirt, but the detergency against various other dirts tends to be lower than that of the powder detergent. In view of this, it is conceivable to add an inorganic builder or an alkali agent that is blended in the powder detergent to increase the detergency against various stains in the liquid detergent. However, since these are solid granular materials, they can be blended with a powder detergent with good dispersibility, but when they are blended with a liquid detergent, they settle and are difficult to disperse uniformly. Therefore, it has been difficult to produce a liquid cleaning agent that uniformly disperses inorganic builder and alkaline agent and stably exhibits excellent cleaning power.

  The present invention has been made in view of the above circumstances, and has advantages of a powder cleaning agent capable of uniformly holding particles such as inorganic builders and alkaline agents, and liquid cleaning such as meterability during use and solubility in washing liquid. The problem is to provide a flowable cleaning agent that combines the advantages of the agent.

（式（１）中、Ｒは炭素数９〜１７のアルキル基またはアルケニル基を示す。ｎはオキシエチレン基の平均繰り返し数を示し、１０〜２０である。）
［３］チューブ状容器、ポンプ式容器、スクイズ容器からなる群より選ばれる１つに、［１］または［２］の流動性洗浄剤が充填されたことを特徴とする容器入り洗浄剤。 As a result of intensive studies, the present inventors have found that a flowable detergent having a property (thixotropic property) in which the viscosity decreases when shear stress is applied and the viscosity increases when no shear stress is applied can solve the above problem. I found it.
The present invention has the following configuration.
[1] A fluid detergent having the following thixotropy index of 5 to 2.
Thixotropic index: Viscosity ratio (ηα / ηβ) of viscosity ηα at a rotational speed of 6 rpm measured at 50 ° C. using a B-type viscometer and a viscosity ηβ at a rotational speed of 30 rpm.
[2] Nonionic surfactant (A) represented by the following formula (1), one or more components (B) selected from polyethylene glycol having a mass average molecular weight of 9000 to 200,000 and methoxylated polyethylene glycol; 1 or more types of (C) component chosen from the group which consists of an alkali agent and an inorganic builder, and water (D) are contained at least, Content of the said (A) component is 40-70 mass%, Said (B) The content of the component is 0.5 to 3% by mass, the content of the component (C) is 10 to 40% by mass, and the content of water (D) is more than 0 and 10% by mass or less. [1] The fluid detergent.

(In formula (1), R represents an alkyl group or alkenyl group having 9 to 17 carbon atoms. N represents the average number of repeating oxyethylene groups and is 10 to 20.)
[3] A container-containing cleaning agent characterized in that one selected from the group consisting of a tube-shaped container, a pump-type container, and a squeeze container is filled with the fluid cleaning agent of [1] or [2].

  According to the present invention, a flow having both the advantages of a powder cleaning agent that can uniformly hold particulates such as inorganic builders and alkaline agents, and the advantages of liquid cleaning agents such as meterability during use and solubility in washing liquid. Can be provided.

Hereinafter, the present invention will be described in detail.
<Cleaning agent>
The fluid detergent of the present invention (hereinafter sometimes simply referred to as a detergent) is a detergent having a thixotropy index of 5 to 2, and exhibits sufficient thixotropic properties.

The thixotropy is a property that when a shear stress is applied, the viscosity is lowered to become a liquid, and when no shear stress is applied, the viscosity is increased to become a paste or a solid.
Since the cleaning agent exhibiting sufficient thixotropy becomes a paste when no shear stress is applied, such as when it is filled in a container, solid particulates can be uniformly dispersed and held in the cleaning agent. That is, a granular alkali agent and an inorganic builder can be maintained uniformly. On the other hand, cleaning agents exhibiting sufficient thixotropy become liquid when shear stress is applied. Therefore, it is easy to squeeze the container filled with the cleaning agent, grip it, or operate the pump to apply shear stress to the cleaning agent during use. It can be weighed and has excellent meterability. Moreover, it is excellent also in the solubility to a washing liquid.
A cleaning agent exhibiting sufficient thixotropy has both the advantages of a powder cleaning agent and the advantages of a liquid cleaning agent.

The thixotropy index (TI value) is a value that serves as an index of thixotropy, and is a viscosity ratio when viscosity is measured at two different rotational speeds using a rotational viscometer.
The thixotropy index in this specification refers to the viscosity ratio (ηα / ηβ) between the viscosity ηα at a rotational speed of 6 rpm and the viscosity ηβ at a rotational speed of 30 rpm measured at 50 ° C. using a B-type viscometer.

  The value of the thixotropic index of the fluid detergent of the present invention is 5 to 2 as described above, and 4 to 3 is preferable. When the thixotropy index is within the above range, the fluid detergent exhibits sufficient thixotropy, and exhibits the advantages of the powder detergent and the liquid detergent.

  The flowable detergent having a thixotropic index within the above range is selected from polyethylene glycol having a specific nonionic surfactant (A) of 40 to 70% by mass, a weight average molecular weight of 9000 to 200,000 and a methoxylated polyethylene glycol. 0.5 to 3% by mass of the component (B) component of one or more species, 10 to 40% by mass of one or more component (C) selected from the group consisting of alkali agents and inorganic builders, and water (D) exceeding 0 A cleaning agent containing at least a mass% or less is mentioned.

[Nonionic surfactant (A)]
Nonionic surfactant (A) (hereinafter sometimes referred to as component (A)) is an ethylene oxide adduct represented by the following formula (1).

  In formula (1), R is a linear or branched alkyl group having 9 to 17 carbon atoms, or a linear or branched alkenyl group having 9 to 17 carbon atoms. n shows the average repeating number of an oxyethylene group, and is 10-20.

  By using the component (A), the detergent tends to exhibit sufficient thixotropy, that is, sufficient thixotropy in which the thixotropy index falls within the above range. In addition, the component (A) is difficult to gel even if it is contained in the cleaning agent at a high concentration, so it can be blended in the cleaning agent at a high concentration and expresses a high cleaning effect with a small amount of the cleaning agent used. It can be used as a cleaning agent.

In the formula (1), when the carbon number of R is less than 9, the detergency is lowered, and when the carbon number of R exceeds 17, the gel easily becomes abrupt. 9-13 are preferable and, as for carbon number of R, 11-13 are more preferable.
Further, when R is within the above range, the detergent tends to exhibit sufficient thixotropic properties.

  In formula (1), n is 10-20, and 12-17 are preferable. When n is within the above range, the detergent tends to exhibit sufficient thixotropic properties.

  Content of (A) component in a cleaning agent is 40-70 mass%. When the component (A) is less than the above range, although depending on the amount and type of other components, the cleaning agent is in a low viscosity state or a high viscosity state, and it is difficult to exhibit sufficient thixotropic properties. Further, it tends to be difficult to obtain sufficient cleaning power as a “concentrated type” cleaning agent. If the component (A) exceeds the above range, the cleaning agent will be in a high viscosity state, and it will be difficult to show thixotropic properties, and although the alkali agent and inorganic builder (C) component can be kept homogeneous, the meterability during use Inferior in solubility in washing liquid. 40-70 mass% is preferable and, as for content of (A) component in a cleaning agent, 50-60 mass% is more preferable.

  The component (A) is usually a mixture of ethylene oxide adducts having different numbers of moles of ethylene oxide (EO) (the number of repeating oxyethylene groups). The component (A) preferably has a narrow ratio of 20% by mass or more, and the substantial upper limit is 80% by mass. The narrow ratio is more preferably 20 to 60% by mass, and further preferably 30 to 45% by mass from the viewpoint of improving the temporal stability at low temperatures. The narrow ratio is represented by the following formula (S), and indicates the distribution ratio of ethylene oxide adducts having different oxyethylene group repeat numbers.

［式中、ｍ_ｍａｘは全体のエチレンオキサイド付加体中に最も多く存在するエチレンオキサイド付加体のオキシエチレン基の繰り返し数を示す。ｉはオキシエチレン基の繰り返し数を示す。Ｙｉは全エチレンオキサイド付加体中に存在する、オキシエチレン基の繰り返し数がｉであるエチレンオキサイド付加体の割合（質量％）を示す。］

[ _Wherein , m _max represents the number of repeating oxyethylene groups of the ethylene oxide adduct most present in the entire ethylene oxide adduct. i represents the number of repeating oxyethylene groups. Yi represents the ratio (% by mass) of the ethylene oxide adduct present in all ethylene oxide adducts and having an i number of repeating oxyethylene groups. ]

  The higher the narrow rate, the better the cleaning power. Moreover, a cleaning agent with few odors originating in the raw material of (A) component is easy to be obtained as a narrow rate is 20 mass% or more, especially 30 mass% or more. This is because, when the narrow ratio is high, the fatty acid ester as the raw material of the component (A) coexisting with the component (A) after the production of the component (A); addition of ethylene oxide of n = 1 and 2 in the formula (1) It is thought that both of the body;

The narrow rate can be controlled by the method for producing the component (A), particularly the kind of the synthesis catalyst used for producing the component (A).
The narrow rate is measured by a conventional method using a reversed phase column in high performance liquid chromatography.

The method for producing the component (A) is not particularly limited, but it is largely a method of transesterification of a fatty acid or a fatty acid methyl ester with a methanol EO adduct; a method of directly adding EO to a fatty acid methyl ester; There are two ways.
The method of directly adding EO to the fatty acid methyl ester is easy, for example, by a method of addition polymerization of EO to the fatty acid alkyl ester using a surface-modified composite metal oxide catalyst as a synthesis catalyst (see Patent Document 2). Can be manufactured.
As the surface-modified composite metal oxide catalyst, specifically, metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , surface modified by a metal hydroxide or the like, La ³⁺ , Mn ^2+, etc.) added to the composite metal oxide catalyst such as magnesium oxide; hydrotalcite calcination catalyst surface-modified with metal hydroxide and / or metal alkoxide, etc. . In addition, a catalyst in which calcium acetate is dispersed in oleic acid and acid-treated with sulfuric acid can be used. The synthesis catalyst is usually removed by filtration or the like after the synthesis of the component (A).

  When a method of addition polymerization of EO to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst as a synthesis catalyst is adopted, the component (B) described below is a byproduct together with the component (A). As a mixture is obtained. In the present invention, this mixture can be used as it is as a component containing the component (A) and the component (B). In that case, as will be described later, a cleaning agent can be obtained by mixing the component (C) and water (D) with a component to be blended as necessary.

[Component (B)]
The cleaning agent of the present invention contains at least one of polyethylene glycol having a mass average molecular weight of 9000 to 200,000 and methoxylated polyethylene glycol having a mass average molecular weight of 9000 to 200,000 as component (B). By combining the component (B) with the component (A) described above and further using water (D) and appropriately adjusting the blending ratio of these components, an appropriate amount of the component (C) described below, which is a solid granular material, is obtained. When added, the detergent exhibits sufficient thixotropic properties. As a result, the component (C) can be uniformly dispersed and held in the cleaning agent, and the measurement property of the cleaning agent and the solubility in the washing liquid are excellent.
The methoxylated polyethylene glycol is one in which one end of polyethylene glycol is methoxylated, both ends are methoxylated, or a mixture of both.
In addition, the mass average molecular weight herein is a value measured by gel permeation chromatography (hereinafter, GPC) using polyethylene glycol having a mass average molecular weight of 2000, 9000, 20000, 200000, 360000 as a standard substance.
If the mass average molecular weight of the component (B) exceeds the above range, the cleaning agent will be in a high viscosity state and it will be difficult to show thixotropy, and the particulate matter such as the component (C) can be held uniformly, but the meterability during use Inferior in solubility in washing liquid. When the mass average molecular weight of the component (B) is less than the above range, the effect of adding the component (B) cannot be obtained, and the cleaning agent does not exhibit thixotropic properties. The weight average molecular weight of the component (B) is preferably 20,000 to 90,000.

  The content of the component (B) in the cleaning agent is 0.5 to 3% by mass, preferably 1 to 2.5% by mass, and more preferably 1.5 to 2.5% by mass. When content of (B) component exceeds the said range, a cleaning agent will be in a state with a high viscosity, and it will become difficult to show thixotropic property. Therefore, although (C) component which is a solid granular material can be hold | maintained uniformly, the measurement property at the time of use and the solubility to a washing | cleaning liquid are inferior. When the content of the component (B) is less than the above range, the effect of adding the component (B) cannot be obtained, and the cleaning agent tends to hardly exhibit thixotropic properties.

  The mass ratio [B / A] of the component (A) and the component (B) is preferably 0.02 to 0.08, more preferably 0.035 to 0.05, from the viewpoint that sufficient thixotropic properties are easily obtained. .

[Component (C)]
The cleaning agent of this invention contains 1 or more types chosen from the group which consists of an alkali agent and an inorganic builder as (C) component. (C) A component is a solid granular material. By containing the component (C), the cleaning agent of the present invention exhibits excellent cleaning power equivalent to that of a powder cleaning agent against various stains. Moreover, since the cleaning agent of the present invention exhibits sufficient thixotropy, the component (C) that is a granular material is uniformly dispersed and retained in the cleaning agent.

  The alkaline agent is not particularly limited as long as it is used for a powder cleaning agent for clothing, for example, carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate. A double salt such as sodium potassium carbonate; a silicate such as sodium silicate and potassium silicate; and an alkanolamine such as monoethanolamine, diethanolamine and triethanolamine. An alkali agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The inorganic builder is not particularly limited as long as it is used, for example, as a powder cleaning agent for clothing. For example, crystalline aluminosilicate (A-type zeolite, P-type zeolite, X-type zeolite, etc.), amorphous Aluminosilicates; orthophosphates, pyrophosphates, tripolyphosphates, metaphosphates, hexametaphosphates, phytates, etc .; crystalline silicates, carbonates and amorphous alkali metal silicates Of the complex. An inorganic builder may be used individually by 1 type, and may be used in combination of 2 or more type.

  Content of the (C) component in a cleaning agent is 10-40 mass%, 15-35 mass% is preferable and 20-30 mass% is more preferable. When the component (C) exceeds the above range, it becomes difficult to uniformly disperse in the cleaning agent, and the cleaning agent hardly exhibits thixotropic properties. When the component (C) is less than the above range, it is difficult to obtain sufficient detergency against various stains.

[Water (D)]
The cleaning agent of the present invention contains water as a component (D) in the range of more than 0% by mass and 10% by mass or less. When the component (D) exceeds 10% by mass, the cleaning agent has a low viscosity, and it is difficult to exhibit thixotropic properties. For this reason, even if the meterability during use and the solubility in the washing liquid are good, the solid particulate matter such as the component (C) tends to settle and cannot be maintained uniformly. On the other hand, if water (D) is not included, the cleaning agent is in a high-viscosity state and is difficult to exhibit thixotropic properties. The lower limit of the component (D) is preferably 1% by mass from the viewpoint of thixotropic expression. As for content of (D) component in a cleaning agent, 2-5 mass% is more preferable.

[Optional ingredients]
The cleaning agent of the present invention can contain optional components such as a surfactant, an enzyme, a bleaching activator, and a fluorescent brightening agent other than the component (A) as necessary.
Examples of the surfactant other than the component (A) include polyoxyethylene alkyl ether which is the same nonionic surfactant as the component (A) and linear alkylbenzene sulfonate which is an anionic surfactant. Can be used. It is also preferable to contain a surfactant other than the component (A) in a range of, for example, 30% by mass or less.

[Production method of cleaning agent]
The cleaning agent of the present invention can be produced by mixing the components (A) to (D) described above and optional components that are blended as necessary.
Moreover, as mentioned above, when the method of addition-polymerizing ethylene oxide to a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst as a method for producing the component (A), together with the component (A) A mixture containing the component (B) as a by-product is obtained. In the present invention, this mixture can be used as it is as the component (A) and the component (B). Further, if necessary, at least a part of the by-product may be removed and the component (B) may be added separately. However, in any case, the content of the component (B) in 100% by mass of the cleaning agent needs to be within the above-described range.

<Cleaning agent in container>
The container-containing cleaning agent of the present invention is obtained by filling one container selected from the group consisting of a tube-shaped container, a pump-type container, and a squeeze container with the above-described cleaning agent.

  The tubular container has a tubular container body that is closed at one end and opened at the other end to serve as a cleaning agent extrusion port, and a screw type, one-touch type cap attached to the extrusion port, By pushing the container body, the cleaning agent in the container body is pushed out from the extrusion port. As the tube-shaped container, a known tube-shaped container disclosed in, for example, JP-A-10-168500 can be used.

  The pump-type container has a container main body and a pump head attached to the upper end opening of the container main body. By pushing the pump head downward, the cleaning agent in the container main body is sucked up, and the nozzle of the pump head It is discharged from. Examples of the pump type container include Japanese Utility Model Publication No. 54-34641, Japanese Utility Model Application Publication No. 56-38883, Japanese Utility Model Application Publication No. 56-46572, Japanese Utility Model Application Publication No. 56-1000037, Japanese Utility Model Application Publication No. 56-121678. Known pump-type containers such as those described in JP-A No. 59-28078 and JP-A No. 2-105900 can be used.

  The squeeze container has a container main body that is deformed by squeeze (squeezing), a discharge port that discharges the cleaning agent in the container main body, and a cap attached to the mouth of the container main body. The container body is deformed by squeezing the body of the container body by hand while being inverted, and the cleaning agent is discharged from the discharge port. In such a squeeze container, when the squeezed state is released, the deformation of the container body is released, and the cleaning agent remaining in the discharge port is returned to the container body by the bag suction mechanism (suction mechanism) at that time. As the squeeze container, for example, a known squeeze container disclosed in JP-A-2002-264958 can be used.

As described above, since the cleaning agent of the present invention exhibits sufficient thixotropy, there are advantages of a powder cleaning agent that can hold a solid granular material uniformly, meterability during use, solubility in washing liquid, etc. Combined with the advantages of liquid detergents.
Therefore, the cleaning agent of the present invention can hold solid particulates such as component (C) in a uniformly dispersed state, and therefore has a high cleaning power and is conventionally used for filling liquid cleaning agents. It can be filled into a container such as a tubular container, a pump-type container, a squeeze container, etc., and can be easily weighed in the same manner as a liquid detergent and put into a washing liquid.

Hereinafter, the present invention will be specifically described with reference to examples.
<Evaluation>
[Evaluation of sebum detergency]
・ Cleaning treatment method 100 pieces of cotton plain weave cloth (uncontaminated cloth) cut into 10cm square and 10 pieces of sebum soiled cloth made by rubbing facial sebum dirt and a commercially available T-shirt (100% cotton, BV The total amount of 2 kg of D. was put into a fully automatic washing machine (trade name: NA-F802P, manufactured by Matsushita Electric Industrial Co., Ltd.).
Then, in accordance with the bath ratio (mass ratio) of 15 times, 15 mL of cleaning agent is dissolved in 30 L of tap water (hardness 3 ° DH) at 20 ° C., washing time is 10 minutes, dehydration is 1 minute, rinse (repeated twice, each 5 minutes) and 1 minute of dehydration as one step.

The reflectance of the sebum-stained cloth (hereinafter referred to as “cleaning cloth”) after the above-described washing operation 1 step was measured with a color difference meter (trade name: SE200 type, manufactured by Nippon Denshoku Co., Ltd.), and the cleaning rate (% ) Was calculated by the following formula.
Washing rate (%) = (K / S of sebum soiled cloth−K / S of washed cloth) / (K / S of sebum soiled cloth−K / S of unsoiled cloth) × 100
In the formula, K / S = (1−R / 100) ² / (2R / 100), where R represents reflectance (%).
(Evaluation criteria)
X: The cleaning rate is less than 60%.
Δ: The cleaning rate is 60% or more and less than 65%.
○: The cleaning rate is 65% or more and less than 70%.
A: The cleaning rate is 70% or more.

[Powder dispersibility]
100 g of detergent was placed in an Empton tube having an inner diameter of 24 mm and a height of 220 mm, and stored at room temperature for 6 months. The appearance at that time was visually evaluated.
X: It has isolate | separated into two layers, the lower layer which contains many (C) components, and the upper layer which hardly contains (C) components.
○: Separation is not recognized.

[Exhaust of cleaning agent from container]
A pump-type container (see FIG. 3 of JP-A-10-168500) used in cosmetic cream or the like is filled with a cleaning agent, and the pump head attached to the upper end opening of the container body is moved downward with a normal force. By manually pressing, the cleaning agent in the container body was sucked up and discharged from the nozzle of the pump head.
(Evaluation criteria)
X: The pump head cannot be pushed in at all.
○: A small amount of detergent composition appears when the pump head is pushed in strongly.
A: When the pump head is pushed in with a normal force, an appropriate amount of the detergent composition is produced.

[Solubility in washing liquid]
Gently stir 5 ° C tap water with a stirrer, add 5 g of detergent at room temperature, stir for 10 minutes, filter this with a nylon mesh, and remove the undissolved detergent on the mesh. After drying at 105 ° C. for 2 hours to evaporate water, the mass of the undissolved cleaning agent was weighed, and the dissolution residue was calculated by the following equation.
Dissolved residue (%) = {weight of cleaning agent remaining undissolved (g) / 5 (g)} × 100
×: 20% by mass or more Δ: 10% by mass or more and less than 20% by mass ○: 5% or more and less than 10% by mass A: Less than 5%

[Thixotropic index]
At 50 ° C., a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used to measure the viscosity ηα at a rotational speed of 6 rpm and the viscosity ηβ at a rotational speed of 30 rpm, and the viscosity ratio (ηα / ηβ) was determined.

<Examples and Comparative Examples>
Each component was mixed by the ratio shown in Table 1-Table 3, the cleaning agent of each example was manufactured, and it evaluated by the above-mentioned method. The results are shown in Tables 1 to 3.
In addition, each component in a table | surface is as follows.

(A-3): Palm fatty acid methyl (mixture of methyl laurate / methyl myristate = 8/2 in mass ratio) added with 15 mol of ethylene oxide using an alkoxylation catalyst [MEE (C12 / 14-15EO)], synthetic product, narrow rate 30%.
In the formula (1), R is an alkyl group having 11 and 13 carbon atoms and a compound having n = 15, and was produced as follows.
Synthesis was performed according to the synthesis method described in Patent Document 2 (corresponding to sample D). 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 was applied at 600 ° C. for 1 hour in a nitrogen atmosphere. A calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by firing, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester Were charged into a 4 L autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 3 × 10 ⁵ Pa, 1052 g of ethylene oxide was introduced and reacted while stirring. Further, 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 then the catalyst and by-products were separated by filtration, and MEE (C12 / 14-15EO). Got.

(A-1), (a-2), (a-4), and (a-5) were produced in the same manner as (a-3) except that the amount of ethylene oxide introduced was changed.
(A-1): A compound in which R is an alkyl group having 11 or 13 carbon atoms and n = 9 in formula (1). Narrow rate 35%.
(A-2): In the formula (1), R is an alkyl group having 11 or 13 carbon atoms, and n = 12. Narrow rate 33%.
(A-4): A compound in which R is an alkyl group having 11 or 13 carbon atoms and n = 20 in formula (1). Narrow rate 28%.
(A-5): A compound in which R is an alkyl group having 11 or 13 carbon atoms and n = 25 in formula (1). Narrow rate 27%.

For (ab-7), (ab-8), and (ab-9), the amount of ethylene oxide introduced was changed, the by-product was not filtered, and only the catalyst was filtered. It was produced in the same manner as 3). In addition, since these components contain the (A) component and the (B) component, they are positioned as “(A) + (B) component”.
(Ab-7): In the formula (1), R is an alkyl group having 11 or 13 carbon atoms, a compound having n = 12, and a polyethylene glycol having a mass average molecular weight of 20,000 or a mixture of a methoxylated polyethylene glycol ( Confirmed by GPC.) The content of polyethylene glycol or methoxylated polyethylene glycol in the (ab-7) component is 1% by mass. Narrow ratio of compound of formula (1) 33%.
(Ab-8): In the formula (1), R is an alkyl group having 11 or 13 carbon atoms, a compound having n = 15, and a polyethylene glycol having a mass average molecular weight of 40,000, or a mixture of methoxylated polyethylene glycol ( Confirmed by GPC.) The content of polyethylene glycol or methoxylated polyethylene glycol in the (ab-8) component is 2% by mass. Narrow ratio of compound of formula (1) 30%.
(Ab-9): In formula (1), R is an alkyl group having 11 or 13 carbon atoms, a compound having n = 20, and a polyethylene glycol having a mass average molecular weight of 70,000 (confirmed by GPC). The content of polyethylene glycol in the (ab-9) component is 2.5% by mass. Narrow ratio of compound of formula (1) 28%.

  (A-6): Manufactured in the same manner as in the above (a-3) except that palm fatty acid methyl was used in place of palm fatty acid methyl and the amount of ethylene oxide introduced was changed. In the formula (1), R is an alkyl group having 15 or 17 carbon atoms, and n = 15.

(B-1): polyethylene glycol having a weight average molecular weight of 8000 (b-2): polyethylene glycol having a weight average molecular weight of 70,000 (b-3): polyethylene glycol having a weight average molecular weight of 210,000

(C-1): Sodium carbonate (c-2): Type A zeolite

AE (C12 / C14-15EO): Coconut higher alcohol added with 15 moles of ethylene oxide LAS: Linear alkylbenzene sulfonate Enzyme: Protease Bleach activator: C8-12 alkanoyloxybenzenesulfonic acid Optical brightener: 4,4′-bis- (2-sulfostyryl) -biphenyl salt

  From the results of Tables 1 to 3, each cleaning agent obtained in the examples shows sufficient thixotropy, so that sebum detergency, powder dispersibility, discharging property of the cleaning agent from the container, and dissolution in the washing liquid It had both the advantages of powder detergent and liquid detergent.

Claims (3)

The following thixotropy index is 5 to 2, and is a fluid detergent.
Thixotropic index: Viscosity ratio (ηα / ηβ) of viscosity ηα at a rotational speed of 6 rpm measured at 50 ° C. using a B-type viscometer and a viscosity ηβ at a rotational speed of 30 rpm. Nonionic surfactant (A) represented by the following formula (1);
One or more (B) components selected from polyethylene glycol having a weight average molecular weight of 9000 to 200,000 and methoxylated polyethylene glycol;
One or more components (C) selected from the group consisting of alkali agents and inorganic builders;
Containing at least water (D),
The content of the component (A) is 40 to 70% by mass, the content of the component (B) is 0.5 to 3% by mass, the content of the component (C) is 10 to 40% by mass, and water (D The flowable detergent according to claim 1, wherein the content is more than 0 and 10% by mass or less.

(In formula (1), R represents an alkyl group or alkenyl group having 9 to 17 carbon atoms. N represents the average number of repeating oxyethylene groups and is 10 to 20.)   A container-containing cleaning agent, wherein one selected from the group consisting of a tube-shaped container, a pump-type container, and a squeeze container is filled with the fluid cleaning agent according to claim 1.