JP2001003100A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition having high detergency to the sebum and stained oils and fats and without forming a film on an opened container, an automatic charge inlet of the detergent and the like. SOLUTION: A liquid detergent composition contains: a nonionic surfactant (A) wherein a number of carbons of a hydrophobic group is 10-16 and an average number of moles of ethylene oxide added is 2-6 and a nonionic surfactant (B) wherein a number of carbons of a hydrophobic group is 10-16 and an average number of moles of ethylene oxide added is 10-25, in a ratio of 30-60 mass % based on the mass of the liquid detergent composition in a total amount of (A) and (B) and in a ratio of (A)/(B)=7/3 to 3/7; and further a polyethylene oxide (C) having a mass-average molecular weight of 400-5,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an excellent detergency for sebum stains originating from the human body and coloring oily stains originating in food, which adhere to clothes as dirt, and is used for automatic opening of containers and washing machines. It does not form a film due to gelation of the liquid surface at the inlet, etc., does not cause separation of the nonionic surfactant phase even at high temperatures, has an appropriate fluidity that is easy to handle as a liquid detergent, and the contents fall during use. The present invention relates to a liquid detergent composition which does not cause contamination and stain around the container. Also, the present invention
The present invention relates to a liquid cleaning composition in a container, comprising: a liquid dispensing container; and the liquid cleaning composition filled in the liquid dispensing container.

[0002]

2. Description of the Related Art Liquid detergents used for washing clothes and the like do not disperse fine particles when used, as in granular detergents, and do not irritate the nose or eyes. And has the advantage that excellent detergency can be obtained even with short-time cleaning. In constituting a liquid detergent, a combination of a non-ionic surfactant having a high lipophilicity and a non-ionic surfactant having a high hydrophilicity is used to wash oily dirt,
The cleaning composition satisfying the rinsing property is disclosed in JP-A-58-93799, JP-A-60-65099, JP-A-60-65100,
It is publicly known as seen in JP-T 8-505413.

[0003]

In the above prior art, when the nonionic surfactant concentration is as high as 30% by mass or more, the cubic phase, hexagonal phase and hexagonal phase are based on the general properties of the nonionic surfactant. Since a high viscosity phase such as a phase is formed and the fluidity is lost, even if an undiluted solution of the detergent composition is directly applied to sebum dirt or oil stain to obtain an excellent cleaning effect, the undiluted detergent solution is sufficient for the dirt. This has the drawback that the desired cleaning effect cannot be obtained. Furthermore, due to the high viscosity, it is difficult to remove from the liquid detergent container, and in the washing conditions of the washing time shortening course of a new type of washing machine, which has recently become widespread, the washing power is not quickly dissolved and the washing power is reduced. Was.

As means for solving this problem, Japanese Patent Laid-Open No.
Japanese Patent No. 255996 discloses a liquid detergent having good solubility by containing a nonionic surfactant having a narrow ethylene oxide addition mole number distribution and an alkanolamine. However, this composition forms a film when the lid of the container is left open and is left unsightly, as well as unsightly, clogging of the container outlet, clogging the automatic detergent inlet of the new washing machine, etc. Had disadvantages.

[0005] It is an object of the present invention to provide a liquid detergent composition which does not form a film in an open container or automatic detergent inlet and does not cause separation of the nonionic surfactant phase even at a high temperature. I do. Further, the present invention, by placing the above-described liquid detergent composition in a container, the liquid detergent composition remaining in the nozzle portion after use is easily collected in the container body,
An object of the present invention is to provide a liquid cleaning composition in a container that does not cause liquid dripping.

[0006]

The liquid detergent composition of the present invention contains the following components (A) to (C) as essential components in the detergent composition, and the content of each component in the composition. Found that a liquid detergent composition having the above characteristics can be obtained by satisfying the following conditions, and completed the present invention. That is, in the present invention, the hydrophobic group has 10 to 1 carbon atoms.
6, a nonionic surfactant (A) having an average addition mole number of ethylene oxide of 2 to 6 and a hydrophobic group having 10 to 16 carbon atoms.
A nonionic surfactant (B) having an average addition mole number of ethylene oxide of 10 to 25, and a total amount of (A) and (B) being 30 to 60 mass based on the mass of the liquid detergent composition. %
And (A) / (B) = 7/3 to 3/7, and further comprising polyethylene glycol (C) having a weight average molecular weight of 400 to 5000. An agent composition is provided.

In the liquid detergent composition in a container according to the present invention, the liquid dispensing container has a nozzle for discharging a content liquid to a nozzle member provided for the container body, and covers the nozzle. The container body or the nozzle member has a cylindrical wall portion that rises upward through a circular nozzle bottom that extends from the base of the nozzle to the periphery, with a circular space between the nozzle and the nozzle body. The cap is attached to the container body or the nozzle member at this annular space so as to form a gap in the range of 0.05 to 2.0 mm between the outer wall surface of the cap and the cylindrical wall portion, and the cylindrical wall is formed. Department or
At least one vertical rib is formed on any one of the outer wall surfaces of the cap, and the liquid cleaning composition is filled in a liquid dispensing container.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention has a hydrophobic group having 10 to 16 carbon atoms, preferably 11 to 14 and an average addition mole number of ethylene oxide of 2 to 6, preferably 4 to 4.
6 is a nonionic surfactant. As the hydrophobic group,
Examples thereof include those using higher alcohols, alkylphenols, polypropylene glycols, higher fatty acids, higher amines, higher fatty acid amides and the like as raw materials. Preferred nonionic surfactants as component (A) of the present invention are represented by the following general formula (I). R ₁ —O— (CH ₂ CH ₂ O) n—H (I) In the formula, R ₁ has 10 to 16 carbon atoms, preferably 11 to 14 carbon atoms.
Is a linear or branched alkyl or alkenyl group, and the average number of moles n of the ethylene oxide group (EO) is 2 to 2.
6, preferably 4-6. Specific alkyl groups include, for example, decyl, undecyl, dodecyl,
Examples include a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group. Examples of the alkenyl group include a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group. R ₁ is preferably a linear or branched alkyl group. The average number of added moles n of ethylene oxide groups (EO) is 2 to 6, preferably 4 to 6. When n is within this range, good detergency is obtained for both sebum stains and colored oily stains. And
This is preferable because the bubbles can be removed during rinsing. Here, the average number of moles added means the number of moles of ethylene oxide reacted with 1 mole of the alcohol used. General formula (I)
Can be used alone or as a mixture of two or more kinds. However, the nonionic surfactant having a high lipophilicity of 2 or 3 and the nonionic surfactant of 4 to 6 are used. The use of an agent in combination is particularly preferred because the stability of the present invention, particularly at low temperatures, is improved.

The nonionic surfactant represented by the general formula (I) may be a commercially available product or a product obtained by a known production method. For example, as a hydrophobic group raw material of a nonionic surfactant, synthetic alcohols obtained by the oxo method such as Diadol (13 carbon atoms; manufactured by Mitsubishi Chemical Corporation) and natural alcohols such as Conol (12 carbon atoms; manufactured by Shin Nippon Chemical Co., Ltd.) It can be obtained by adding ethylene oxide to alcohol. The raw material alcohol can be used by mixing, for example,
Ethylene oxide may be added to a mixture of two or more alcohols. The distribution of the number of moles of added EO can be controlled, for example, by distilling a nonionic surfactant to obtain only a predetermined fraction, or the Al ³⁺ described in JP-B-6-15038. , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , L
a ³⁺ , can be narrowed by adding ethylene oxide to an aliphatic alcohol or the like using a specific alkoxylation catalyst such as magnesium oxide to which a metal ion such as Mn ²⁺ is added, or It can also be widened by adding ethylene oxide to an aliphatic alcohol or the like using a normal alkali catalyst such as sodium hydroxide or potassium hydroxide. The addition distribution of ethylene oxide in the nonionic surfactant (A) is, for example, a high performance liquid chromatography using ZOROBAX C8 (manufactured by DuPont) as a column and a mixed solvent of acetonitrile and water as a mobile phase. (HPLC).

The component (B) of the present invention has a hydrophobic group having 10 to 16, preferably 11 to 14, carbon atoms and an average addition mole number of ethylene oxide of 10 to 25, preferably 12 to 2,
0 is a nonionic surfactant. As the hydrophobic group,
As with the component (A) of the present invention, higher alcohols, alkylphenols, polypropylene glycols, higher fatty acids,
Examples thereof include those using higher amines, higher fatty acid amides and the like as raw materials. Preferred as the component (B) of the present invention is a nonionic surfactant represented by the following general formula (II). R ₂ —O— (CH ₂ CH ₂ O) m—H (II) In the formula, R ₂ has 10 to 16 carbon atoms, preferably 11 to 14 carbon atoms.
Is a linear or branched alkyl or alkenyl group, and the average number of added moles m of the ethylene oxide group (EO) is 10
-25, preferably 12-20. Specific examples of the alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group. Examples of the alkenyl group include a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group. R ₂
Is preferably a linear or branched alkyl group.

The average number m of added ethylene oxide groups (EO) is from 10 to 25. If the value of m is within this range,
In particular, the sediment cleaning power of the obtained liquid detergent composition is improved, and the storage stability of the product at low temperatures is also improved. The nonionic surfactant represented by the general formula (II) may be a commercially available product or a product obtained by a known production method. The distribution of the number of moles of ethylene oxide added to the nonionic surfactant of the formula (II) is similar to that of the nonionic surfactant of the formula (I). May be obtained by performing an addition reaction of ethylene oxide to an aliphatic alcohol or the like using a common alkali catalyst such as common sodium hydroxide or potassium hydroxide. The distribution may be wide. The total amount of the nonionic surfactant of the component (A) and the nonionic surfactant of the component (B) is usually 30 based on the mass of the liquid detergent composition.
-60 mass%, preferably 35-50 mass%. Within this range, the solubility and fluidity of the liquid detergent composition are good, and the detergency for sebum stains and colored oily stains is high. (A) in the liquid detergent composition of the present invention
The mixing ratio of the nonionic surfactant of the component and the nonionic surfactant of the component (B) is preferably (A) /
(B) = 7/3 to 3/7, more preferably 6/4 to 4 /
6. Within this range of the mixing ratio, it shows good detergency against both more hydrophobic colored oil and fat stains and slightly less hydrophobic fatty acid sebum stains, and at the same time, the storage stability of the liquid detergent composition. Is also good, which is preferable.
When the component (A) having a different n value is used in combination, the mixing ratio of the nonionic surfactant having a smaller n value to the nonionic surfactant having a larger n value is preferably 1/9 to 6 / by mass ratio.
4, more preferably 2/8 to 4/6. It is preferable that the mixing ratio is within the range, since the detergency for applying oil stains is good and the stability of the composition at low temperatures is good.

The component (C) of the present invention has a weight average molecular weight of 4
It is a polyethylene glycol (PEG) having a weight average molecular weight of 450 to 3,000. When polyethylene glycol having a mass average molecular weight within this range is blended, (A)
Excellent ability to prevent the formation of a film on the surface of the composition at a high concentration of the component and the nonionic surfactant of the component (B), and excellent ability to penetrate the undiluted detergent solution when the undiluted liquid detergent composition is applied to dirt. Detergent power can be demonstrated. Further, such polyethylene glycol is preferable because it has high water solubility and does not precipitate in the composition. In addition, the polyethylene glycol component (C) has the effect of preventing the property that the nonionic surfactant separates as a concentrated liquid phase when the liquid detergent product is left in a high-temperature environment, and the storage stability of the liquid detergent product. Is significantly improved. Specifically, the composition of the present invention does not undergo phase separation when left at 50 ° C., or even 60 ° C. Further, it has an effect of keeping the viscosity when the liquid detergent composition is taken in and out of the container within a range that is easy to use. Specifically, the viscosity of the present invention at 5 ° C. measured using a Brookfield viscometer is 100
0 mPa · s or less, preferably 950 mPa · s or less. Preferred polyethylene glycol used in the present invention,
PEG # 500, PEG # 1000 or PEG # 200
0 or a low molecular weight polyethylene glycol compound,
Such compounds are commercially available. The polyethylene glycol as the component (C) in the present invention can be used alone or as a mixture, and the total amount is usually 1 to 20% by mass, preferably 3 to 15% by mass, based on the mass of the liquid detergent composition. % By mass. This range is preferable because good film formation preventing ability and good solubility can be obtained.

[0013] The composition of the present invention comprises the above components (A) to
Water and the following optional components can be added to (C). In the present invention, an alkali agent such as an alkanolamine can be blended in order to improve the detergency of the liquid detergent composition. As the alkanolamine, for example, an alkanolamine represented by the following formula can be suitably used. (HO-R ₃ ) _p -NH _(3-p) (III) (R ₃ represents an alkylene group, and p represents an integer of 1 to _3. ) In the above formula, as the alkylene group as R ₃ Is
An alkylene group having 1 to 5, preferably 1 to 3 carbon atoms can be suitably used. The alkylene group may have a branch. Specifically, preferred alkylene groups include, for example, a methylene group, an ethylene group, and a propylene group. As p in the above equation,
Preferably, it is 1 or 2. As specific examples of the alkanolamine, preferably, monomethanolamine, monoethanolamine, diethanolamine, triethanolamine and the like can be used. The compounding amount of the alkanolamine is usually 1 to 10% by mass, preferably 2 to 7% by mass, based on the mass of the liquid detergent composition. Within this range, the effect of improving detergency against oily stains and protein stains can be obtained, and at the same time, hypochlorite ions in the washing solution are captured to prevent the inactivation of the enzyme.

In the present invention, an alkaline protease enzyme can be blended in order to improve the detergency of stains containing a large amount of proteins and coloring components, especially blood and milk cocoa. The alkaline protease enzyme is not particularly limited as long as it is an alkaline protease conventionally used in a liquid detergent composition, and various alkaline protease enzymes can be used. Preferred alkaline proteases include, for example, Alcalase (Al
calase) (trademark), Savinase (trademark),
Durazayme ™, Evalase (Eva
lase), Maxatase,
Maxapem (trademark) and the like. Such alkaline proteases are generally preferably used in a total amount of 0.1 to 3% by mass, preferably 0.2 to 1% by mass, based on the mass of the liquid detergent composition. As the enzyme stabilizer used in the present invention,
Any enzyme stabilizer conventionally used in liquid detergent compositions can be used without particular limitation. Examples of such an enzyme stabilizer include boric acid, borax, formic acid, polyols such as ethylene glycol, propylene glycol, and sorbitol, calcium chloride, calcium carbonate, calcium salts such as calcium sulfate, and the like, or a combination thereof. And the like. The amount of the enzyme stabilizer used is usually 0.005 to 10 based on the mass of the liquid detergent composition.
It is suitable to use it in an amount of from 5% by weight, preferably from 0.01 to 5% by weight.

[0015] In addition to the above components, various additives conventionally used in liquid cleaning compositions can be incorporated into the liquid cleaning composition of the present invention without any particular limitation. Examples of such additives include the following. (1) a linear or branched alkylbenzene sulfonate having a hydrophobic chain having 8 to 16 carbon atoms, an alkyl sulfate or an alkenyl sulfate having a hydrophobic chain having 10 to 20 carbon atoms,
Olefin sulfonate having a hydrophobic chain having 10 to 20 carbon atoms, alkane sulfonate having a hydrophobic chain having 10 to 20 carbon atoms, having a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 on average
/9.9 to 9.9 / 0.1 alkyl ether sulfate or alkenyl ether sulfate, having 10 to 2 carbon atoms
Alkyl ethers having 0 linear or branched alkyl or alkenyl groups and having an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide or ethylene oxide / propylene oxide = 0.1 / 9.9 to 9.9 / 0.1 Carboxylate, or alkenyl ether carboxylate, alkyl polyhydric alcohol ether sulfate such as alkyl glyceryl ether sulfonate having 10 to 20 carbon atoms, higher fatty acid salt having 10 to 20 carbon atoms, 8 to 20 carbon atoms Anionic surfactants such as saturated or unsaturated α-sulfofatty acid salts or methyl, ethyl or propyl esters thereof, amino acid surfactants, and N-acyl amino acid surfactants such as acyl sarcosinates. (2) Amphoteric surfactants such as alkyldimethylaminoacetate betaine, dimethylhexadecylcarboxymethylammonium betaine and dimethylhexadecylsulfopropyleneammonium betaine having a hydrophobic chain having 8 to 16 carbon atoms. (3) Hydrotropes such as short-chain alkylbenzene sulfonates, lower alcohols, polyhydric alcohols, and the like. (4) Enzymes other than protease, such as amylase, cellulase, and lipase. (5) Foam control agents such as silicone. (6) fluorescent agents, fragrances, antioxidants, antibacterial agents and the like.

When washing clothes using the liquid detergent composition of the present invention, the clothes may be applied directly to the clothes, or may be dissolved in water and dipped in the clothes. Of course, the clothes may be directly washed with a washing machine or the like without being immersed. When dissolving the liquid detergent composition of the present invention in water and immersing clothing, the total amount of (A) and (B) in the washing bath is 0.05 to 5% by mass, preferably 0.05 to 0.5% by mass, And it is good to dilute so that the amount of the component (C) is 0.02 to 2% by mass, preferably 0.02 to 0.2% by mass. When washing with a washing machine or the like, the total amount of (A) and (B) in the washing bath is 0.01 to 1% by mass, preferably 0.01 to 0.1% by mass, and (C)
0.004 to 0.4% by mass of the component, preferably 0.004 to 0.04%
It is preferable to use it after diluting so as to be mass%.

As an example, the liquid detergent composition of the present invention has a nozzle member fixed to the top of a container body, and a detachable cylindrical cap for covering the nozzle is provided detachably at a distance from the nozzle. It is preferable to fill the liquid solution discharging container. This type of liquid dispensing container itself is already widely used in liquid products filled with liquids such as liquid chemicals, liquid foods, liquid detergents and liquid bleaching agents, and is well known. However, the features of the nozzle member and the cap having a cylindrical shape according to the present invention are that the dripping from the cap mounting portion, which has been a problem in the conventional similar type, is significantly improved. .

Referring to FIG. 1, in a liquid cleaning composition 100 in a container according to the present invention, a liquid dispensing container 110 is provided.
Includes a container body 112, a nozzle member 114, and a cap 116. The nozzle member 114 is connected to the container body 112.
Or it is fixed to the top of the container body 112. Nozzle member 1
14 is a nozzle 11 for discharging the liquid detergent composition.
8 inclusive. The nozzle 118 is connected to the spout 1 disposed at the tip.
18a and a base 118b. Nozzle member 114
Further comprises a nozzle bottom 120 and a nozzle male thread 124
And a nozzle female screw portion 126. A through hole 128 is provided in the nozzle bottom 120. Lock tooth mechanism 112f
Is provided on the container body 112.

The cap 116 has a cylindrical shape with a lid. The cap 116 is provided detachably from the nozzle member 114. The cap 116 includes a lid 116a,
Cap female screw portion 116b, cap outer wall surface 116c
And a flange 116d. Cap female thread 11
6b is located on the outer periphery of the flange 116d. The male screw portion 124 of the nozzle member 114 is screwed into the female screw portion 116b of the cap 116, and can cover the vicinity of the tip of the nozzle 118.

The nozzle member 114 has a cylindrical wall portion 134 which rises upward from a base portion 118b of the nozzle 118 via an annular nozzle bottom portion 120 extending around and forms an annular space 130 with the nozzle 118. As a modification, the cylindrical wall portion 134 may be formed on the container body 112. The cap 116 is located at the annular space 130.
0.05 between the cap outer wall surface 116c and the cylindrical wall portion 134
It is attached to the nozzle member 114 so as to form a gap 160 within a range of up to 2.0 mm. When the cap 116 is attached to the nozzle member 114, the cap outer wall surface 116c
Is configured to face the cylindrical wall portion 134. The tapered portion 118t is formed by the cylindrical wall portion 134 and the nozzle male screw portion 1
24 is formed. An upper space 162 is provided between the cap outer wall surface 116c and the nozzle male screw portion 124 and between the flange 116d and the tapered portion 118t.

At least one, in the illustrated example, two vertical ribs 140, 142 are formed inside the cylindrical wall portion 134, and at least one vertical rib 144 is formed in the nozzle 11
8 is preferably formed outside the cylindrical portion.

The liquid detergent composition 150 of the present invention is filled in the container main body 112 of the liquid agent dispensing container 110. When a container having such characteristics is filled with the liquid detergent composition of the present invention and used, the liquid detergent composition remaining in the nozzle portion after use is easily collected in the container body, causing liquid dripping. There is no advantage.

The liquid detergent composition of the present invention is preferably filled in a thin plastic container which leads to a reduction in the amount of plastic material to be discarded, from the viewpoint of reducing the burden on the environment in recent years. As such a thin plastic container, a container formed by a biaxial stretching method using a polypropylene material and having a wall thickness of 0.1 to 0.3 mm is preferable. Such a thin-walled plastic container generally has a low strength against deformation, so that the container may be deformed when the contents absorb oxygen gas in the head space. This is preferable because no deformation occurs. From a similar viewpoint, it is also preferable that the liquid detergent composition of the present invention is filled in a self-supporting storage bag of a multilayer film composed of various plastic material thin films.

According to the present invention, a conventional nonionic surfactant having a high lipophilicity and a nonionic interface having a high hydrophilicity have a detergency against human-derived sebum and food-derived colored oils and fats adhering to clothes as stains. It is significantly higher than the combination with the surfactant, and does not form a film in open containers or automatic detergent inlets, and the nonionic surfactant phase separates from the composition under various storage conditions, or significantly increases. A liquid detergent composition that does not stick and does not cause liquid dripping during use can be obtained.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 [Production Example] In the following Examples and Comparative Examples, the following nonionic surfactants were used. A component a1; a non-ion obtained by adding 2 moles of ethylene oxide to a branched chain higher alcohol having 13 carbon atoms (Diadol 13, manufactured by Mitsubishi Chemical Corporation, linear ratio 60%) using an alkoxylation catalyst. Surfactant (unreacted alcohol 13
%) A2; a non-ion obtained by adding 5 mol of ethylene oxide to a higher alcohol containing a branched chain having 13 carbon atoms (manufactured by Mitsubishi Chemical Corporation, Diadol 13, 60% linearity) using an alkoxylation catalyst. Surfactant (unreacted alcohol 1%
A3; a non-alkylated product obtained by adding 5 mol of ethylene oxide to a higher alcohol having a branched chain having 13 carbon atoms (Diadol 13, manufactured by Mitsubishi Chemical Corporation, linear ratio 60%) using a sodium hydroxide catalyst. Ionic surfactant B component b1; 15 mol of ethylene oxide is added to a higher alcohol containing a branched chain having 13 carbon atoms (Diadol 13, manufactured by Mitsubishi Chemical Corporation, linear ratio 60%) using an alkoxylation catalyst. Nonionic surfactant (unreacted alcohol 1
B2; 15 mol of ethylene oxide was added to a branched chain higher alcohol having 13 carbon atoms (Diadol 13, manufactured by Mitsubishi Chemical Corporation, linear ratio 60%) using a sodium hydroxide catalyst. Nonionic surfactant

The polyethylene glycol used in the following Examples and Comparative Examples is as follows. c1; PEG # 1000 (degree of polymerization; 23) c2; PEG # 1540 (degree of polymerization; 35) c3; PEG # 200 (degree of polymerization; 5) The alkaline protease enzymes used in the following examples are as follows. . Enzyme x; Durazyme 16L (manufactured by NOVO Nordisk) Enzyme y; Evalase 16L (manufactured by NOVO Nordisk) Enzyme z; Maxapem 30L (manufactured by Genencor) The components were mixed according to the formulations described in Tables 1 and 2 below, and a liquid detergent was used. A composition was prepared.

[Evaluation Method of Detergency] A 100 cm cotton plain woven cloth was cut into a 10 cm square, fixed to the surface of a small container having a hemispherical surface with a radius of about 3 cm, and rubbed on the hand or face. This caused dirt to adhere. Next, this cloth was cut into four equal parts to obtain a sebum stain cloth. Cut a 60 cm cotton plain woven cloth into 5 cm squares, apply 0.2 mL of chili oil (manufactured by Kadoya Oil Co., Ltd.) on one piece of the cloth, apply it to the cloth, rinse thoroughly with running tap water and air-dry overnight. An oil-and-fat soiled cloth was used. Then, using a fully automatic washing machine manufactured by Matsushita Electric Industrial Co., Ltd., "Aizumago NA-F60HP1", one cotton underwear sewn with the above-mentioned ten sebum stain cloths and five colored oily stain cloths, and a Sebum cloth,
2 kg of washed cotton underwear was put in and washed with a standard course.
0.1 mL of the liquid detergent composition stock solution is applied to the sebum stain cloth and the colored oil stain cloth before starting the washing, and the washing is started after standing for 5 minutes, so that the final concentration of the liquid detergent in the washing liquid is 0.08%. The amount of liquid detergent added was adjusted in the same manner. In Tables 1 and 2, the detergency of the sebum soiled cloth obtained by the above-described cleaning method was expressed as the sebum dirt cleaning power, and the detergency of the colored oily soiled cloth was expressed as the colored oily soil detergency. The detergency was calculated according to the following equation. Detergency (%) = (K / S of contaminated cloth−K / S of cleaning cloth) / (K / S of contaminated cloth−K / S of uncontaminated cloth) × 100 where K / S = (1-R / 100) ² / (2R / 100) (where R is the reflectance (%)).

In the following examples, the cleaning rate (%) obtained by the above-described cleaning method and calculation method is shown as a result of classification according to the following criteria. Sebum dirt cleaning power 90% or more: ◎ 80-90%: ○ 70-80%: △ 70% or less: × Colored oil and dirt cleaning power 80% or more: ◎ 70-80%: ○ 60-70%: △ 60% ×: [Evaluation method of ability to prevent film formation] 5 g of the liquid detergent composition shown in Tables 1 and 2 was weighed in a petri dish having a diameter of 5 cm, and left indoors. The degree of film formation on the liquid surface was determined according to the following criteria. ：: No film was observed on the surface even after standing for 24 hours or more. ×: A film is observed after standing for about 1 hour. [Measurement Method of Composition Viscosity] Using a Brookfield viscometer manufactured by Tokyo Keiki Co., Ltd., the viscosities of the liquid detergent compositions shown in Tables 1 and 2 at 5 ° C. were measured with a No. 1 or No. 2 rotor. [Evaluation Method of Storage Stability of Composition] The liquid detergent compositions of Tables 1 and 2 were sealed in a polypropylene resin detergent container, and 6
The composition was allowed to stand in a thermostat at 0 ° C. for 3 days, and the appearance of the composition was evaluated according to the following criteria. ：: Uniform and transparent without separation of the concentrated liquid phase of the nonionic surfactant ×: Separation of the concentrated liquid phase of the nonionic surfactant was observed The above results are summarized in Tables 1 and 2 below. . still,
Table 3 shows specific examples of the fragrance composition.

[0028]

[Table 1] Note) The pH of the composition was adjusted to 10 with an aqueous sulfuric acid solution.

[0029]

[Table 2] Note) The pH of the composition was adjusted to 10 with an aqueous sulfuric acid solution.

[0030]

[Table 3]

Example 2 The various compositions shown in Table 1 of Example 1 are filled in a liquid dispensing container having a nozzle member and a covered cylindrical cap shown in FIG. 1, and the contents are discharged from the container into the cap. After the operation was repeated 50 times, the outer periphery of the container was observed, and no adhesion of the liquid detergent composition was observed at all. Example 3 The various compositions shown in Table 1 of Example 1 were filled in the following thin plastic container and a self-supporting storage bag composed of a multilayer film, and the container was left at 50 ° C. for one month, and the appearance of the container and the properties of the contents were measured. Upon observation, no deformation of the container or any viscosity, odor or discoloration of the contents was observed. Thin plastic container: Material: Polypropylene (biaxially stretch molded) Injection port diameter: 24 mm Body outer diameter: 65.1 mm Capacity: 500 mL Average wall thickness: 0.2 mm Self-supporting storage bag: Material: Stretched nylon / low-density polyethylene / stretched polyethylene Bottom width: 90mm Bottom depth: 55mm Top width: 110mm Average wall thickness: 0.2mm

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a liquid cleaning composition in a container according to the present invention.

FIG. 2 is a schematic side view showing the appearance of a liquid cleaning composition in a container according to the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 liquid cleaning composition in container 110 liquid dispensing container 112 container main body 112 f lock tooth mechanism 114 nozzle member 116 cap 116 a lid 116 b cap female thread 116 c cap outer wall surface 116 d flange 118 nozzle 118 a spout 118 b base 118 t taper 120 nozzle Bottom part 124 Nozzle male screw part 126 Nozzle female screw part 128 Through hole 130 Annular space 134 Cylindrical wall part 140 Vertical rib 142 Vertical rib 144 Vertical rib 150 Liquid detergent composition 160 Gap 162 Upper space

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasumasa Kimura 1-3-7, Honjo, Sumida-ku, Tokyo F-term in Lion Corporation (reference) 3E014 PA01 PB03 PC03 PE17 4H003 AC08 BA12 BA21 DA01 DB02 EA03 EB14 EB36 EC02 FA16 FA28 FA30

Claims (4)

[Claims] 1. A nonionic surfactant (A) having a hydrophobic group having 10 to 16 carbon atoms and an average addition mole number of ethylene oxide of 2 to 6; A nonionic surfactant (B) having an average addition mole number of 10 to 25, wherein the total amount of (A) and (B) is 30 to 60% by mass based on the mass of the liquid detergent composition. And (A) / (B) = 7/3 to 3/7, and further comprising polyethylene glycol (C) having a weight average molecular weight of 400 to 5000. object. 2. The liquid detergent composition according to claim 1, wherein the nonionic surfactant (A) has an average addition mole number of ethylene oxide of 4 to 6. 3. The liquid detergent composition according to claim 1, wherein no phase separation occurs at 60 ° C., and the viscosity at 5 ° C. measured with a Brookfield viscometer is 1000 mPa · s or less. 4. A nozzle for discharging a content liquid to a nozzle member provided for the container main body, a cap for covering the nozzle is provided detachably, and the container main body or the nozzle member comprises: A cylindrical wall portion that rises through an annular nozzle bottom that extends from the base of the nozzle to the periphery and that extends upward with an annular space between the nozzle and the nozzle, and the cap includes:
At this annular space, attached to the container body or the nozzle member so as to form a gap in the range of 0.05 to 2.0 mm between the outer wall surface of the cap and the cylindrical wall portion, the cylindrical shape 4. A liquid dispensing container in which at least one vertical rib is formed on one of a wall portion and an outer wall surface of the cap, and the liquid dispensing container is filled. 1
A liquid detergent composition in a container, comprising: the liquid detergent composition according to any one of the preceding claims.