JP2002167600A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain liquid detergent composition which hardly forms bubbles in cleaning, is excellent in rinsability and in capability for cleaning sebum dirt due to coating, and has a stable clear homogeneous appearance. SOLUTION: This detergent composition contains (a) 5-40 mass% nonionic surfactant which is represented by formula (I): R-O-(EO)n-H (wherein R is a 10-20C alkyl or alkenyl; EO is ethylene oxide unit; and (n) is the number of moles of ethylene oxide added) provided the average number of moles of ethylene oxide added is 2-10, (b) a 14-18C saturated fatty acid or its salt in an amount (in terms of a saturated fatty acid) of 0.1-2.0 mass%, (c) a protease preparation, and (d) a citrate, provided that an anionic surfactant other than a fatty acid salt derived from component (b) is not substantially contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition for use as a detergent for clothing.
The present invention relates to a liquid detergent composition which has a low foaming property at the time of washing, has a good rinsing property, good sebum dirt application detergency, and has a transparent and uniform appearance even during storage.

[0002]

2. Description of the Related Art Liquid detergents used for washing clothes are excellent in that they have better solubility than powder detergents, and that a high cleaning effect can be obtained by directly applying them to dirt. In general, builders such as zeolite that are blended into powder detergents are difficult to blend in liquid detergents, so alkyl ether sulfates and nonionic surfactants that have excellent hard water resistance are mainly used. ing. However, since these surfactants have excellent hard water resistance, they have good foaming properties even at relatively low concentrations, and are inferior in rinsing properties to alkylbenzene sulfonates and alkyl sulfates usually used in powder detergents. Conventionally, it is known to incorporate a fatty acid salt into a detergent composition to improve rinsing properties. For example, a fatty acid salt is added to a detergent composition containing an anionic surfactant and a nonionic surfactant as a main base material. And JP-A-61-2880.
No. 00 publication. However, when the anion surfactant is used as a main base material, the foam tends to be excessively formed during washing, and when used in a washing machine that easily foams such as a drum-type washing machine that has begun to spread in recent years in Japan, There is a concern that bubbles may overflow during washing. JP-A-4-63900 describes a liquid detergent composition containing a nonionic surfactant and soap and having a low foaming property at the time of washing without an anionic surfactant other than soap. However, 5% by mass or more of soap is required to satisfy the low foaming property, and when such an amount of soap is blended, the viscosity of the composition at a low temperature becomes remarkable, and there is a problem in usability in winter. .

[0003] On the other hand, the object of cleaning in a detergent for clothing is mainly sebum dirt attached to a collar or a sleeve. However, since this is a composite dirt of oil and protein, it is usually difficult to use only a dilute solution of a surfactant having a cleaning concentration. It is difficult to remove sufficiently, and it is effective to apply a liquid detergent stock solution directly to dirt, or to mix a protease which is a proteolytic enzyme into the detergent. However, in the case of a liquid detergent, since the liquid protease preparation used generally contains a calcium salt or the like for stabilizing the preparation, when the protease preparation and a fatty acid or a salt thereof are blended together as a foam regulator, Calcium salts of fatty acids and the like are precipitated, which may cause a problem in uniformity of the detergent composition.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid detergent for clothing which has low foaming properties during washing, has excellent rinsing properties, excellent sebum dirt application detergency, and has uniform transparent appearance stability. Another object of the present invention is to provide an inexpensive liquid detergent composition.

[0005]

Means for Solving the Problems The present inventors have solved the above-mentioned problems by a liquid detergent composition comprising a combination of a specific nonionic surfactant, a specific saturated fatty acid or a salt thereof, a protease preparation and citrate. And completed the present invention. That is, the present invention provides (a) represented by the following general formula (I):

Embedded image R—O— (EO) n—H (I) (R: alkyl or alkenyl group having 10 to 20 carbon atoms, EO: ethylene oxide, n: number of moles of ethylene oxide added) Average of ethylene oxide 5 to 40% by mass of nonionic surfactant having an addition mole number of 2 to 10 (b) 0.1 to 2.0% by mass of saturated fatty acid having 14 to 18 carbon atoms or a salt thereof in terms of saturated fatty acid (c) Protease Formulation (d) The present invention provides a liquid detergent composition characterized by containing a citrate salt and substantially free of an anionic surfactant other than the fatty acid salt derived from the component b.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) nonionic surfactant is represented by the general formula (I), wherein R has 10 to 10 carbon atoms.
20, preferably an alkyl group or an alkenyl group having 12 to 18 carbon atoms, and an alkyl group having 12 to 15 carbon atoms is particularly preferable from the viewpoint of detergency. The average number of moles of ethylene oxide added is 2 to 10, preferably 3 to 8, and 4 to 6
Is particularly preferred. It is preferable that the number of moles of ethylene oxide added be within this range, since the sebum stain application detergency and the rinsing property are excellent. The molar distribution of addition of ethylene oxide is defined as a ratio of the total content of the nonionic surfactant in the range of ± 2 moles before and after the average number of moles of ethylene oxide added to the total mass of the nonionic surfactant as a narrow ratio. Then, the narrow ratio is preferably 55% or more, and 65% or more.
% Or more is more preferable. It is preferable that the addition molar distribution of ethylene oxide be within this range because the sebum stain application detergency and the rinsing property are excellent. The method for producing a non-ionic surfactant having a high narrow ratio is not particularly limited, and a reaction product having a low molecular weight within a necessary molecular weight range is separated from a reaction product having a low narrow ratio obtained by adding ethylene oxide by a conventional method. It is obtained by doing. Further, for example, by using the method described in Japanese Patent Publication No. 6-15038, a nonionic surfactant having a high narrow ratio can be easily obtained.
The narrow ratio can be easily measured by using high performance liquid chromatography. In the present invention, the amount of the component (a) is 5 to 4 in the liquid detergent composition.
0% by mass, and preferably in the range of 10 to 30% by mass. It is preferable for the component (a) to be within this range because the sebum stain application detergency, rinsing properties and economic efficiency are excellent. The nonionic surfactant (a) may be used alone or in combination of two or more.

As the component (b), a saturated fatty acid having 14 to 18 carbon atoms or a salt thereof is used. Here, as the salt,
Alkali metal salts of fatty acids, alkanolamine salts, lower alkylamine salts, ammonium salts and the like are used.
Specific examples thereof include myristic acid, palmitic acid, stearic acid, and a saturated fatty acid having 14 to 18 carbon atoms.
Hardened tallow fatty acid which is a mixture of 4-18 saturated fatty acids,
Hardened palm oil fatty acid, or a salt thereof, diethanolamine palmitate, diethanolamine stearate, hardened tallow fatty acid diethanolamine, hardened palm oil fatty acid diethanolamine, and the like can be used alone or in combination of two or more. Good. In the present invention, among these, palmitic acid, stearic acid, hydrogenated tallow fatty acid, hydrogenated palm oil fatty acid and its salts such as diethanolamine palmitate, diethanolamine stearate, hydrogenated tallow fatty acid diethanolamine, and hydrogenated palm oil diethanolamine are low foam. It is preferable from the viewpoints of properties, rinsing properties and appearance stability. In the present invention, the compounding amount of the component (b) is 0.1 to 2.0% by mass, preferably 0.5 to 1.0% by mass in terms of saturated fatty acid in the liquid detergent composition. is there.
When the component (b) is within this range, low foaming properties, rinsing properties,
It is preferable because it has excellent appearance stability and economy. Especially 2.
If it exceeds 0% by mass, the viscosity of the composition at low temperatures becomes remarkable, causing a problem in usability. Further, the saturated fatty acid or the salt thereof of the component (b) may be used alone or in combination of two or more.

[0008] The protease preparation (c) has a detergency-improving effect on sebum stains, and in particular, a high effect can be obtained with a relatively small amount by mixing and washing with a liquid detergent. As a protease preparation, for example, Savi
case16L (NovoNordisk), Du
razym16L (manufactured by Novo Nordisk),
Everlase16L (manufactured by NovoNordisk), Purafect L (manufactured by GENENCOR), Purafect OX 4000L (GENE)
NCOR), Properase L (GENEN)
COR company). In the present invention, (c)
The compounding amount of the component is preferably 0.1% in the liquid detergent composition.
It is in the range of 1 to 1.0% by mass, more preferably 0.2 to 0.5% by mass. It is preferable for the component (c) to be within this range because the sebum stain application detergency and economic efficiency are excellent. Further, even when the protease preparation of the component (c) is used alone,
Two or more kinds may be used in combination.

Examples of the citrate of component (d) include alkali metal salts such as sodium and potassium, and alkanolamine salts such as diethanolamine and triethanolamine. Of these, trisodium citrate is particularly preferred. In the present invention, the amount of the component (d) is preferably 0.01 to 1.0 in the liquid detergent composition.
%, More preferably 0.05 to 0.5% by mass. It is preferable for the component (d) to be within this range because the appearance stability and economic efficiency are excellent. The ratio (c) / (d) of the amount of the component (c) to the amount of the component (d) is 1
0/1 to 1/5 are preferred, and 5/1 to 1/2 are more preferred. It is preferable that (c) / (d) is within this range because the appearance stability and economic efficiency are excellent. The citrate of the component (d) may be used alone or in combination of two or more.

[0010] Further, the liquid detergent composition of the present invention includes:
(B) Anionic surfactants such as higher fatty acid salts other than the fatty acid salt derived from the component, alkylbenzene sulfonates, alkyl sulfates, olefin sulfonates, and alkyl ether sulfates have low foamability and appearance stability during washing. It must not be blended from the point of.

The liquid detergent composition of the present invention may contain an alkali agent to improve the detergency during normal use. Examples of the alkaline agent include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide.Alkanolamines are preferable, and among them, diethanolamine and triethanolamine are preferable. Amines are particularly preferred. The compounding amount of the alkaline agent is preferably in the range of 0 to 10% by mass, more preferably 0.5 to 5% by mass in the liquid detergent composition.

When the average addition mole number of ethylene oxide of the nonionic surfactant (a) is 5 or less, the composition of the present invention may contain (a) ) A nonionic surfactant other than the component can be blended. As the nonionic surfactant, carbon number 1
A polyoxyethylene alkyl ether having an average addition mole number of ethylene oxide of 11 to 30, having an alkyl group of 0 to 18, an alkyl group having 8 to 18 carbon atoms, and having an average addition mole number of the glucose unit of 1 to 10; Alkyl polyglucoside, having an alkyl group having 10 to 14 carbon atoms, alkyl glyceryl ether having an average addition mole number of 1 to 3 glycerin units, fatty acid diethanolamide having 10 to 20 carbon atoms, and having an alkyl group having 10 to 20 carbon atoms. And methoxypolyoxyethylene alkanoates having an average addition mole number of 1 to 30 of ethylene oxide, and the like, among which, having an alkyl group having 12 to 15 carbon atoms,
Polyoxyethylene alkyl ethers having an average addition number of ethylene oxide of 12 to 20 are particularly preferred. The amount of these nonionic surfactants is preferably 0 to 40% by mass, more preferably 5 to 3% by mass in the liquid detergent composition.
The range is 0% by mass. The total amount of these nonionic surfactants and the nonionic surfactant of the component (a) is calculated based on the total mass of the liquid detergent composition of the present invention.
Preferably 10 to 60% by mass, more preferably 20 to 4% by mass.
0% by mass.

The liquid detergent composition of the present invention further comprises, as other components, ethylene glycol, propylene glycol, polyethylene glycol for stabilizing at a low temperature.
Glycol solvents such as polypropylene glycol
10% by mass, polyvinylpyrrolidone to prevent recontamination,
0 to 2% by mass of a re-contamination inhibitor such as carboxymethylcellulose and soil release polymer, 0 to 1% by mass of enzymes such as lipase, amylase and cellulase for improving detergency other than sebum stains, and dimethyl for improving texture 0 to 5% by mass of silicone such as silicone, polyether-modified silicone and amino-modified silicone; 3 to 10% by mass of hydrotrope such as sodium paratoluenesulfonate and ethanol for stabilization at low temperature; whiteness of white clothing 0 to 1% by mass of a fluorescent agent such as distyrylbiphenyl type for improvement, 0.00001 to 0.001% by mass of a dye such as an acid dye for coloring the liquid detergent composition, and stabilization of aroma. Antioxidant such as dibutylhydroxytoluene to 0.00
01-0.5% by mass, caisson CG / IC for preservative
0 to 0.03% by mass of an antibacterial agent such as P can be blended. As a fragrance for fragrance, Japanese Patent Application No. 2000-3
No. 46626, and a fragrance composition (A to D) containing a solvent and a stabilizer for the fragrance is 0.1 to 0.5.
% By mass.

The liquid detergent composition of the present invention can be contained in a plastic container. Examples of the plastic container include a main container and a standing pouch for refilling. As the main body container, the container described in Japanese Patent Application No. 11-356440 or Japanese Patent Application No. 11-356442 is preferable. Further, as a standing pouch, for example, JP-A-2000-72181
The materials described therein include a two-layer structure of a linear low-density polyethylene of 100 to 250 μm in the inner layer and a stretched nylon of 15 to 30 μm in the outer layer, or
From the viewpoint of storage stability, a three-layer standing pouch in which a stretched nylon of μm is an intermediate layer and a stretched nylon of 15 μm is an outer layer is preferable.

[0015]

Industrial Applicability According to the present invention, a liquid detergent composition which is low-foaming during washing, excellent in rinsing properties, sebum dirt application detergency and transparent and uniform appearance stability as a detergent for clothing. Things can be provided at a lower cost.

[0016]

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Examples and comparative examples are shown below to specifically explain, but prior to this, an evaluation method adopted will be described.

1) Evaluation method of low foaming property and rinsing property 30 L of tap water (25 ° C., 4 ° DH) was put into a washing tub of a two-tub washing machine (CW-C30A1-H, manufactured by Mitsubishi Electric Corporation), and placed there. 20 g of the liquid detergent composition of Table 1 and a cotton skin shirt (BV
D) (1 kg), and stir with a standard water flow for 10 minutes. The low foam property was evaluated by measuring the height of the foam from the water surface 30 seconds after the stirring was completed. For the low foam property, the height of the foam was evaluated according to the following criteria. ○: Foam height of less than 5 cm △: Foam height of 5 cm or more and less than 10 cm ×: Foam height of 10 cm or more Then, after dewatering the cotton skin shirt in a dewatering tank for 1 minute, tap water (25 ° C., (4 ° DH) into a washing tub containing 30 L, and stirred with a standard water flow for 3 minutes. This dehydration and stirring operation was repeated once, and the rinsing property was evaluated by observing the remaining state of bubbles on the water surface 30 seconds after the completion of stirring.
The rinsing property was evaluated based on the following criteria for the remaining state of the foam. Rinsing ◎: Foam film (5 mm or more and less than 1 cm) remains on the water surface 50% or less ○: Foam film (5 mm or more and less than 1 cm) remains on the water surface 50% or more and less than 100% ×: Foam film (5 mm or more) (Less than 1 cm) remains on the entire surface of the water, or bubbles (1 cm or more) remain

2) Evaluation method of sebum dirt application and detergency A plain cotton woven cloth (# 100) of 10 cm × 10 cm is placed on the surface of a small container having a hemispherical surface with a radius of about 3 cm, with the hemispherical portion at the center of the cloth. Then, the hemispherical portion was rubbed against the face to attach dirt, thereby producing a sebum soiled cloth. For evaluation, the sebum-stained cloth was cut into four equal parts around the stain. The liquid detergent composition of Table 1 was applied to 10 pieces of the cut sebum soiled cloth so as to spread over the entire area of the soil at a rate of 0.06 g / sheet, and allowed to stand for 5 minutes. After standing, the sebum soiled cloth was washed with tap water at 120 rpm using tap water (25 ° C.,
Washing was performed for 10 minutes under a condition of 900 ml (4 ° DH), rinsed for 3 minutes, and finally dried using an iron. In the following examples, the sebum dirt application detergency is determined by measuring the Z value of the original cloth before and after the dirt is adhered and the sebum dirt cloth before and after the cleaning using a colorimetric colorimeter (manufactured by Nippon Denshoku Co., Ltd .: SE2000). (Table 1 shows the average value of the cleaning rates of 10 sheets). Cleaning rate (%) = (Z value after cleaning−Z value before cleaning) / (Z value of original cloth−Z value before cleaning) × 100

3) Evaluation method of appearance stability 750 ml of the liquid detergent composition shown in Table 1 was used for 15 cm in width.
(Width of bottom 12cm when spread), depth of bottom 7.
5cm, height 26cm, 800ml volume, 15 from inside
It is housed and sealed in a standing pouch having a three-layer structure of 0 μm linear low-density polyethylene / 15 μm stretched nylon / 15 μm stretched nylon, left at 20 ° C. for 30 days, and then discharges the composition into a 1 L beaker to give an appearance. Observed and evaluated. The appearance stability was evaluated according to the following criteria. Appearance stability ○: Uniform and transparent ×: Precipitate

Examples 1 to 5 and Comparative Examples 1 to 6 A liquid detergent composition having the composition shown in Table 1 was prepared. The appearance stability was evaluated. The results are shown in Table 1. In addition, the compounding quantity in a table | surface is a mass%.

[0021]

[Table 1]

The details of the components used in Table 1 are as follows. Component (a) Nonionic surfactant Nonionic surfactant 1a: straight-chain primary alcohol ethoxylate having 12 carbon atoms (average number of moles of ethylene oxide added: 2, narrow ratio: 93%, JP-A-2000-6130)
Using the catalyst of Example 1 in JP-A-4, 190 g of ethylene oxide introduced in Reaction Evaluation Method I of the same publication
Non-ionic surfactant 2a: straight-chain primary alcohol ethoxylate having 12 carbon atoms (average number of moles of ethylene oxide added: 5, narrow ratio) : 42%, EMALEX 705, manufactured by Nippon Emulsion Co., Ltd.) Nonionic surfactant 3a: C12 to C13 branched chain primary alcohol ethoxylate [average number of moles of ethylene oxide added: 5, narrow ratio: 86%] JP 200
Using the catalyst of Example 1 in JP-A-61304, lauryl alcohol 40 of reaction evaluation method I of the same publication was used.
0 g of Dovanol 23 (manufactured by Mitsubishi Chemical Corporation) 418
g, the amount of ethylene oxide introduced was 473 g, and the reaction was carried out. After the reaction was completed, 17.6% of purified water was added to the crude reaction product, and 0.12% of Hyflo Super Cell (manufactured by Celite) as a filter aid After stirring at 80 ° C. for 30 minutes, the catalyst and the auxiliary agent were separated by filtration to obtain a nonionic surfactant content of 85%, manufactured by Lion Chemical Co., Ltd.). In addition, the compounding amount of this sample in the examples is a compounding amount as 100% conversion of the nonionic surfactant. Nonionic surfactant 4a: straight-chain primary alcohol ethoxylate having 12 carbon atoms (average number of moles of added ethylene oxide: 7, narrow ratio: 39%, EMALEX707, manufactured by Nippon Emulsion Co., Ltd.) Ionic surfactant Nonionic surfactant 5: Branched primary alcohol ethoxylate having 13 carbon atoms [average number of moles of added ethylene oxide: 15, narrow ratio: 33%, diadol 13]
(Manufactured by Mitsubishi Chemical Corporation) by adding ethylene oxide using KOH as a catalyst, manufactured by Lion Chemical Corporation]

Fatty acid of component (b) Fatty acid 1b: palmitic acid (NAA-160, manufactured by NOF Corporation) Fatty acid 2b: hardened tallow fatty acid (C ₁₆ / C ₁₈ = 45 /
55, Riptor CY-1000, manufactured by NOF CORPORATION) (b) Fatty acids other than the component Fatty acid 3: Oleic acid (extra olein 99, manufactured by NOF CORPORATION) (c) Protease preparation of component Savinase 16L: Novo Nordisk
16L Everose: Novo Nordisk
Citrate of component (d) Citric acid / 3Na: Purified sodium citrate L (manufactured by Fuso Chemical Co., Ltd.) Optional component Anionic surfactant: Sodium linear alkyl ether sodium sulfate having 12 carbon atoms (ethylene oxide Average number of added moles: 3, Teicapol NE1230, manufactured by Teica Co., Ltd.) Diethanolamine: diethanolamine (manufactured by Mitsui Chemicals, Inc.) Triethanolamine: triethanolamine 99 (manufactured by Dow Chemical Company) Polyethylene glycol: mass average molecular weight 1000 ( P
EG # 1000, manufactured by NOF CORPORATION) Na paratoluenesulfonate: SODIUM P-TO
LUEN SULFONATE (Dah Ding C
chemical Industry Co. , Ltd.
Ethanol) 95% denatonium benzoate modified ethanol Fragrance composition: Tables 11 to 11 of Japanese Patent Application No. 2000-346626.
18. A fragrance composition A to D dye described in 18: Quinoline Yellow WG-G CONC (Chuo Gosei Chemical Co., Ltd.)

As is clear from Table 1, the liquid detergent compositions of the present invention (Examples 1 to 5) have a low foaming property during washing,
And it has excellent rinsing properties, sebum stain application detergency, and appearance stability. When any of these is missing (Comparative Examples 1 to
6) is a good low-foaming property, rinsing property, detergency for applying sebum dirt,
It can be seen that all of the appearance stability cannot be satisfied.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/386 C11D 3/386 F term (Reference) 4H003 AB03 AC08 AC22 BA12 DA01 EB08 EB14 EB22 EB36 EC02 ED02 ED28 FA16 FA19 FA23

Claims (1)

[Claims] (A) represented by the following general formula (I): ## STR1 ## R--O-(EO) n--H (I) (R: alkyl or alkenyl having 10 to 20 carbon atoms) Group, EO: ethylene oxide, n: addition mole number of ethylene oxide) 5 to 40% by mass of nonionic surfactant having an average addition mole number of ethylene oxide of 2 to 10 (b) saturated fatty acid having 14 to 18 carbon atoms or 0.1 to 2.0% by mass of the salt in terms of saturated fatty acid (c) Contains a protease preparation (d) citrate and substantially does not contain an anionic surfactant other than the fatty acid salt derived from the component b. A liquid detergent composition comprising: