JP2000109886A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid detergent composition that has detergency suitable for clothes made of delicate fabrics, especially clothes made of silk and wool, and causes a washing liquid to become whitened according to the degree of the soil removal while washing the laundry by blending an ethylene oxide-added nonionic surfactant, a cationic surfactant which is difficult to be soluble in water, an anionic polymer constituting the main chain of a polysaccharide and a water-soluble inorganic or organic salt into the composition. SOLUTION: A nonionic surfactant of formula I and a cationic surfactant of formula II that is difficult to be soluble in water are employed. In formula I, R1 is a 10-22C alkyl or alkenyl, or an alkylphenyl having 6-12C alkyl; and (n) is 5-15. In formula II, at least one of R2-R5 is independently a 12-24C alkyl or alkenyl and the others are each methyl or ethyl, provided that each of R2-R5 includes a group substituted or interrupted by a functional group such as OH, O, CO-NH, COO or the like; and X denotes a halogen, CH3SO4 or C2H5SO4. As an example of an anionic polymer constituting the main chain of a polysaccharide, a carboxymethylcellulose is most preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid detergent capable of performing practical washing even in a soaked laundry, and more particularly to clothing which needs to be washed even with a slight stain such as silk products, wool products and fashionable clothes. On the other hand, the present invention relates to a liquid detergent composition which has a practical detergency by immersion washing, and in particular, makes it possible to feel the stain removal at the time of washing because the washing liquid becomes cloudy according to the removal of the stain even if the stain is slightly removed.

[0002]

2. Description of the Related Art In recent years, dry cleaning has become a major environmental problem due to the use of a large amount of solvents that have an adverse effect on the environment, such as chlorofluorocarbons, parks, petroleum, and the like. A point that has recently attracted attention. However, fashionable clothes, especially silk products and wool products, are usually washed by a normal washing method (specifically, a washing method with a mild current in a washing machine, or a manual operation such as squeezing or pushing). Method), dry cleaning must be performed to remove stubborn oil stains. Therefore, Japanese Patent Application Laid-Open No. 5-51598 describes a new dry cleaning solvent using a glycol ether-based solvent, and reports that environmental safety and removal of water-soluble stains have been improved. It has been done. However, removal of water-soluble stains is still insufficient as compared with water-based washing, and solvent-based dry cleaning has not yet been sufficiently solved.

Further, as a softener composition excellent in the feel and shape retention function of clothing, Japanese Patent Application Laid-Open No. 1-250473 discloses a liquid softener composition which imparts flexibility with a cationic surfactant and an anionic polymer. No. 5,058,058, but no detergency is described for these compositions.

[0004] For this reason, there has been a demand for a washing method and a washing agent which are excellent in the feeling and form retention function of clothes and also excellent in the washing function for fashionable clothes, especially silk products and wool products by washing with water. JP-A-7-54264,
JP-A-6-313193, JP-A-8-48993
JP, JP-A-8-48994 and JP-A-8-4994
No. 8995 discloses that an oily stain which is difficult to remove by washing in an aqueous system in which a water-soluble solvent is mixed with a neutral transparent liquid detergent having a basic skeleton of a nonionic surfactant and a cationic surfactant is easily removed. A dedicated liquid detergent composition is disclosed, and JP-A-10-88195 further discloses that a hardly water-soluble solvent is further blended to remove stubborn oil stains that could only be removed by dry cleaning. There is disclosed a liquid detergent composition that can be easily removed, and has a high dirt-removing effect on both water-soluble stains and stubborn oil stains.

However, in these liquid detergent compositions, the degree of turbidity of the washing liquid in accordance with the removal of stains is not enough to realize the removal of the stains, so that the removal of the stains cannot be confirmed and the cleaning effect cannot be realized. Moreover, once the used washing liquid is reused, there is a possibility that the dirt once removed may be attached again. On the other hand, Japanese Patent Application Laid-Open No. 1-132892 and US Pat. No. 3,928,213 disclose a nonionic surfactant,
Although a liquid detergent composition containing a cationic surfactant and an anionic polymer is described, the washing liquid becomes cloudy as the stain is removed, so that you can feel the stain removal. No description is given of the agent composition.

[0006] From the above background, even a small amount of dirt is surely dispersed in the washing liquid, and the washing liquid becomes cloudy as the dirt is removed, so that the dirt removal can be realized. There is a need for an agent composition.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a liquid washing method which has a practical detergency for fashionable clothes, especially silk products and wool products, and in which the washing liquid becomes cloudy in accordance with stain removal during washing. It is intended to provide an agent composition.

[0008]

Means for Solving the Problems Based on the above-mentioned problems, the present invention has been studied diligently.

[0009]

Embedded image In the formula, [R ₁ is a linear or branched alkyl group and alkenyl group having 10 to 22 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 12 carbon atoms, and n is 5 to 15]. Agent, (B) Formula (2):

[0010]

Embedded image Wherein independently R _2, R _3, R ₄ and R ₅ together are which at least one alkyl or alkenyl group having 12 to 24 carbon atoms, the remainder methyl, ethyl, these R ₂ to R ₅ are each optionally -OH, -O -, - CO- N
Also included are those substituted or interrupted by a functional group such as H-, -COO-. X represents a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO ₄ . One or more kinds of poorly water-soluble cationic surfactants represented by the formula (C):
Anionic polymer whose main chain is composed of polysaccharide (D)
An object of the present invention is to provide a liquid detergent composition containing a water-soluble inorganic or organic salt.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant represented by the formula (1) used in the present invention is a nonionic surfactant of an ethylene oxide addition type, and has an alkyl group and an alkenyl group having 10 to 22 carbon atoms or a carbon number of 10 to 22 carbon atoms. One or more of these polyoxyethylene alkyl or alkenyl ethers having an alkylphenyl group having 6 to 12 alkyl groups and 5 to 15 moles of ethylene oxide added can be used. The compounding amount is 10 to 50% by weight, preferably 15 to 40% by weight based on the total amount of the composition. If the amount is less than 10% by weight, not only the detergency is weak, but also the stability at low temperatures is reduced. On the other hand, if it is added in an amount exceeding 50% by weight, the solubility at room temperature is poor and a gel is formed, which is not preferable.

The poorly water-soluble cationic surfactant represented by the formula (2) used in the present invention is one or more quaternary ammonium salts, and at least one of the long-chain alkyls has at least one carbon atom. Is 12 to 24, preferably 16 to 20
Is an alkyl group or an alkenyl group. These long-chain alkyls are each optionally -O-, -CO-NH-, -COO
-And the like. When the carbon number of the long-chain alkyl is less than 12, sufficient flexibility and texture cannot be obtained in the washed fabric, and when the carbon number exceeds 24, the stability at low temperatures is reduced. Further, from the viewpoint that the stain removal can be realized more, two or more long-chain alkyls are preferable.

The other alkyl groups are a methyl group and an ethyl group, each of which is optionally OH, --O--, --CO--NH.
It may be substituted or interrupted by a functional group such as-or -COO-, but is preferably a methyl group. X is a halogen atom such as chlorine, bromine or iodine, CH ₃ S
O ₄ or C ₂ H ₅ SO ₄ , preferably chlorine.

Further, the poorly water-soluble cationic surfactant in the present invention means a surfactant having a solubility in water at 20 ° C. of 1% or less. Specific examples include di-hardened tallow alkyl dimethyl ammonium chloride, di-tallow hardened alkyl dimethyl ammonium bromide, dioleyl dimethyl ammonium chloride, dipalmityl methyl hydroxyethyl ammonium methyl sulfate, distearyl methyl polyoxyethylene (average degree of polymerization of 3 moles). )
Ammonium chloride, diisostearyldimethylammonium chloride, dibehenylmethylpolyoxyethylene (average degree of polymerization 5 mol) ammonium chloride,
Dielsyldimethylammonium chloride, di [(2
-Dodecanoylamino) ethyl] dimethylammonium chloride, di [(2-stearoylamino) propyl] dimethylammonium ethyl sulfate, di (2
-Ethyl palmitoyl) hydroxyethyl methyl ammonium methyl sulfate, trioleyl methyl ammonium chloride, dioleyl monostearyl methyl ammonium chloride, dioleyl monobehenyl methyl ammonium chloride, monooleyl eryl methyl ammonium chloride, tristearyl methyl ammonium methyl sulfate, etc. Alternatively, a mixture of two or more kinds is mentioned, and the most preferred specific example is dioleyl dimethyl ammonium chloride.

[0015] The compounding amount of these poorly water-soluble cationic surfactants is 1 to 15% by weight, preferably 2 to 15% by weight, based on the total amount of the composition.
-10% by weight. When the amount is less than 1% by weight, flexibility is not imparted to the washed fiber, and when the amount exceeds 15% by weight, the low-temperature stability is impaired, and the detergency is reduced.

Specific examples of the anionic polymer having a main chain composed of a polysaccharide used in the present invention include sodium carboxymethylcellulose, potassium carboxymethylcellulose, sodium alginate, potassium alginate, sodium guluronate, sodium mannuronate,
Examples include sodium pectate and sodium galacturonate. These may be used not only in one kind but also in a mixture of two or more kinds.
Carboxymethyl cellulose.

The anionic polymer whose main chain is composed of a polysaccharide is 0.01 to 1.0% by weight, preferably 0.05 to 0.5% by weight, more preferably 0 to 1.0% by weight based on the total amount of the composition. 0.05 to 0.1% by weight. The amount is 0.01
When the amount is less than 1.0% by weight, cloudiness of the washing liquid hardly occurs. When the amount is more than 1.0% by weight, the stability of the liquid detergent composition is impaired, and the liquid detergent composition becomes a high-viscosity liquid, which poses a problem in practical use.

The water-soluble inorganic or organic salt used in the present invention may be any of an inorganic acid salt and an organic acid salt. May be prepared from an acid and an alkali. As salts of inorganic acids,
Salts such as sodium, potassium, ammonium, etc., sulfates, nitrates, carbonates, bicarbonates, borates and the like, and salts of organic acids include citrate, benzoate, succinate, lactate The most preferred specific examples include sodium chloride and sodium sulfate as salts of inorganic acids, and sodium citrate as salts of organic acids. One or more of these salts can be used, and the compounding amount is preferably 1.0% by weight or less, particularly preferably 0.1% by weight or less. A blending amount of 1.0% by weight or less is preferable from the viewpoint of stability. When the blending amount is 0.01% by weight or less, it becomes difficult to discriminate the white turbidity of the washing liquid according to the stain degree.

The composition of the present invention can be produced by a conventional method, and is preferably used as a low-viscosity (5-500 cp; B-type viscometer, spindle # 2) liquid detergent.

In the present invention, as long as the effects of the present invention are not impaired, conventionally known semipolar surfactants such as amine oxides,
Amphoteric surfactants such as alkyl betaine, organic solvents (eg, alcohols such as propanol, glycol ethers, etc.), fragrances, enzymes (eg, enzymes such as protein hydrolase, lipid hydrolase, starch hydrolase, Bacteriolytic enzymes, etc.), bactericides, dyes and the like can also be appropriately compounded. In the liquid detergent of the present invention, in order for the above-mentioned effect to be more clearly exhibited, the washing liquid concentration is set to 0.1.
Preferably it is 1 to 50% or less. Further, the effect of the present invention appears regardless of the bath ratio.

[0021]

EXAMPLES The present invention will be described in more detail with reference to Examples. Needless to say, the present invention is not limited to these Examples, and unless otherwise specified, [%] represents [% by weight]. Examples and comparative examples shown in Table 1 were prepared by a conventional method, and evaluated by a washing liquid turbidity test and a soaking test. Table 1 shows the results. In addition, tap water was used for each test.

<Evaluation Method> Washing liquid turbidity test The turbidity of the washing liquid after washing was evaluated with reference to “1.4.2 Evaluation method of detergency using artificially stained cloth” described in the latest washing technology overview, page 326. 5 cm × 5 in 1000 ml of a 0.1% aqueous solution of the liquid detergent shown in each of Examples and Comparative Examples.
5 cm wet artificial soiled cloth of the Washing Science Association
After immersion washing for 5 minutes, the washing liquid before washing was compared with the washing liquid, and the degree of cloudiness of the washing liquid after washing was visually compared.
The results are shown in Table 1. The cleaning conditions are as follows. <Washing conditions> Cleaning time 15 minutes Liquid detergent composition 0.1% Cleaning temperature 25 ° C <Evaluation criteria> ：: White turbidity occurs X: No white turbidity occurs

2. Soak cleaning test 1. The detergency of the artificially wet contaminated cloth (hereinafter referred to as “cleaning cloth”) used in the washing liquid turbidity test was evaluated by the following method. The artificial wet-type soiled cloth before cleaning is the contaminated cloth, and the original cloth before the artificial contaminated cloth is made the cleaned cloth. The surface reflectance of the cleaning cloth, the contaminated cloth, and the cleaning cloth was measured, and the cleaning rate was calculated by the following equation. The surface reflectance was measured with a colorimeter ZE-2000 (manufactured by Nippon Denshoku Industries). The washing cloth was sandwiched between towels, dehydrated, and completely dried before use in order to adjust the experimental conditions. The results are shown in Table 1.

[0024]

[Number 1] detergency ratio _{(%) = (R W -R} S / R O -R S) × 100 R O: surface reflectance of the clean cloth R _S: surface reflectance of the stained cloth R _W: the surface of the cleaning cloth Reflectivity The cleaning rate is shown as an average value of 5 sheets, and 25% or more is considered to have an effect higher than usual.

[0025]

[Table 1]

As shown in Table 1, a formulation containing the nonionic surfactant of the present invention, a poorly water-soluble cationic surfactant, an anionic polymer whose main chain is composed of a polysaccharide, and an inorganic salt or an organic salt was prepared. In Examples 1 to 4), it was found that the washing liquid became cloudy after soaking washing. On the other hand, a formulation containing an anionic polymer whose main chain is composed of other than polysaccharide (Comparative Examples 1 and 2) and a formulation containing a cationic or nonionic polymer whose main chain is composed of polysaccharide (Comparative Examples 3 and 4), the formulation containing no polymer (Comparative Example 5), and the formulation containing no poorly water-soluble cationic surfactant (Comparative Example 6) did not cause washing clouding. Was. Further, all of the liquid detergents of the formula of the present invention exhibited excellent detergency.

3. Correlation test between the concentration of dirt in the washing liquid and the turbidity of the washing liquid The correlation between the concentration of dirt in the washing liquid and the turbidity of the washing liquid is evaluated by the following method by putting the model soil into the washing liquid. did. Five washing liquids (0.1% aqueous solution, 100 ml) having the formulations of Example 1 and Comparative Example 5 shown in Table 1 were prepared. 0 mg, 100 mg, and 200 mg of model soil prepared with a composition obtained by removing carbon black and mud, which are particle stains, from the soil used for wet artificial soiling cloth of the Washing Science Association in the prepared washing liquid. , 300mg,
Each 500 mg was mixed into the washing liquid. The L value indicating the lightness of the washing liquid was measured by a colorimeter ZE-2000 (manufactured by Nippon Denshoku Industries) by a transmission method, and the turbidity of each washing liquid was calculated by the following equation. When the turbidity of the washing liquor calculated by the following equation was 15 or more, the turbidity of the liquor could be visually confirmed.

[0028]

Laundry liquid turbidity = (100−La) − (100−Lo) La: color difference value L in the washing liquid after mixing of model soil Lo: color difference value L in the washing liquid before mixing of model soil Are shown in Table 2. The reason why the particle stain is removed as the model stain is to clarify the turbidity of the washing liquid that occurs together with the intended stain.

[0029]

[Table 2] As shown in Table 2, it was confirmed that the formulation of the present invention (Example 1) became cloudy according to the concentration of the model soil in the washing liquid, whereas the formulation without the anionic polymer was confirmed. In (Comparative Example 5), only slight cloudiness was generated in accordance with the concentration of the model soil, which was such that cloudiness could not be visually confirmed. Therefore, it was recognized that the liquid detergent composition of the present invention caused the washing liquid to become cloudy in accordance with the removal of dirt during washing with care.

[0030]

The liquid detergent composition of the present invention has a practical detergency and a form-retaining function for washing silk products, wool products, fashionable clothes, and the like. Due to the cloudiness, even a slight stain can be realized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 17/08 C11D 17/08

Claims (3)

[Claims] (A) Formula (1): [Wherein, R ₁ is a linear or branched alkyl group and alkenyl group having 10 to 22 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 12 carbon atoms, and n is 5 to 15]
A nonionic surfactant represented by the formula (B): Formula (2): Wherein independently R _2, R _3, R ₄ and R ₅ together are which at least one alkyl or alkenyl group having 12 to 24 carbon atoms, the remainder methyl, ethyl, these R ₂ to R ₅ are each optionally -OH, -O -, - CO- N
Also included are those substituted or interrupted by a functional group such as H-, -COO-. X represents a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO ₄ . And (C) an anionic polymer having a main chain composed of a polysaccharide, (D) a water-soluble inorganic salt or organic salt. A liquid detergent composition characterized in that the washing liquid becomes cloudy in response to stain removal. 2. The amount of (A) the nonionic surfactant is 10 to 50% by weight, (B) the poorly water-soluble cationic surfactant is 1 to 15% by weight, and (C) the total amount of the composition. The amount of the anionic polymer whose main chain is composed of a polysaccharide is 0.01 to 1.0% by weight, and the amount of the water-soluble inorganic or organic salt (D) is 0.01 to 1. 2. The liquid detergent composition according to claim 1, which is 0% by weight. 3. The liquid detergent composition according to claim 1, which is a liquid detergent for clothing for soaking washing.