JPH06313193A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. which has a strong detergency and is exclusively used for immersion washing by mixing a specific cationic surfactant, a nonionic surfactant, a semipolar surfactant, and a glycol ether solvent in a specified wt. ratio. CONSTITUTION:This detergent compsn. is prepd. by mixing 1-5wt.%. cationic surfactant of formula I (wherein R<1> and R<2> are each 12-24C alkyl or alkenyl; R<3> and R<4> are each methyl, ethyl, etc.; and X is halogen, CH3SO4, etc.) having an iodine value of 40-100 (e.g. dioleyldimethylammonium chloride), 10-30wt.%. nonionic surfactant of formula II (wherein R<5> is 10-20C alkyl, alkenyl, etc.; and (n) is 5-15) (e.g. a polyoxyethylene mixed-alkyl ether), 0.5-8wt.%. semipolar surfactant of formula III (wherein R<6> is 10-22C alkyl; and R<7> and R<8> are each methyl, ethyl, etc.), and 1-70wt.%. glycol ether solvent of formula IV (wherein R<9> is 1-4C alkyl; R<10> is 1-2C alkylene; and R<11> and R<12> are each H or methyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent liquid cleaning agent which is exclusively used for placing. More specifically, the present invention has practical cleaning power and shape retention function for clothes such as silk products, wool products, fashionable clothes, etc. that require cleaning even with slight stains, and does not impair excellent texture. In addition, the present invention relates to a neutral transparent liquid detergent composition which is excellent in storage stability and is exclusively used for washing by putting it on.

[0002]

2. Description of the Related Art Conventional washing is generally called pre-washing before washing in a washing machine, hand-washing (fir-washing), etc., and putting it in a detergent solution containing enzymes to enhance the washing power. Was pointing at. Therefore, for a long time (for example,
If you don't put it on overnight, it won't get rid of enough stains. Therefore, if you wear silk or wool clothing for such a long time, the clothing will shrink.

[0003] That is, for washing clothes at home, after washing with a detergent containing an anionic surfactant or a nonionic surfactant as a main component, in order to impart a texture and an antistatic ability to fibers, Although a softening agent containing a cationic surfactant as a main component is used for further softening treatment, this method requires two operations of washing and imparting flexibility, which is complicated. Therefore, Japanese Patent Publication No. 47-475
No. 0 and JP-A-57-126896,
A one-pack type cleaning method in which the above two operations are performed at the same time has been studied.

This one-pack type composition mainly comprises a nonionic surfactant or a semipolar surfactant as a main component, and a monoalkyl or dialkyl type cationic surfactant having a long-chain saturated group in the molecule as a softener component. It is compounded as. This system is transparent at room temperature at the beginning of formulation, but if it is stored for a long period of time, it will precipitate an insoluble substance, or will cause clouding or precipitation at low temperatures, significantly reducing the commercial value. As a result, in terms of performance, there is a problem in stability while maintaining an appropriate cleaning power and texture. Therefore, in JP-A-4-4298 and JP-A-4-153300, a one-pack type cleaning method has an appropriate cleaning power, does not impair an excellent texture, and is excellent in storage stability. A description of a transparent liquid detergent is given.

However, silk products, wool products, fashionable clothes, etc. are washed by a normal washing method (specifically, a washing method with a mild water flow in a washing machine or a hand operation such as curling or pushing). Method), the garment after washing contracts or loses its shape, which significantly reduces the commercial value of the garment. Therefore, in order to prevent the shrinkage and deformation of the clothing, the putting-on-and-leasing method is adopted. However, the above-mentioned cleaning agents have insufficient cleaning power, and in particular, they are effective for removing stains that are partially conspicuous such as stains. Inferior. Further, for silk products, wool products, fashionable clothes, etc., there is a demand for a cleaning method and a cleaning agent which are excellent in the texture and shape retention function of clothes and also in the cleaning function.

[0006]

The present invention differs from the conventional soaking and washing in that it takes a very short time, for example, 10 to 3
A cleaning agent that removes dirt without shrinkage of delicate clothes such as silk or wool by 0 minutes soaking, and wash and finish well, that is, silk products,
It has practical washing power and shape retention function for wool products, fashionable clothes, etc., and it gives excellent flexibility and texture to the clothes after washing, and it is also stable for room temperature and low temperature. It aims at providing a transparent liquid cleaning agent.

[0007]

The present invention provides the formula (I):

[0008]

[Chemical 5]

(In the formula, R ¹ and R ² have 12 to 24 carbon atoms.
An alkyl group or an alkenyl group, R ³ and R ⁴ are a methyl group, an ethyl group, a polyoxyethylene group or a polyoxypropylene group, and X is a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO ₄ ) One or a mixture of two or more selected from the compounds shown, having an iodine value of 4
1-5% by weight of a cationic surfactant of 0-100 and the formula (II):

[0010]

[Chemical 6]

(Wherein, R ⁵ is an alkyl or alkenyl group having 10 to 20 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 12 carbon atoms, and n is 5 to 15) 10 to 30% by weight of surfactant, and formula (III):

[0012]

[Chemical 7]

(Wherein R ⁶ represents an alkyl group having 10 to 22 carbon atoms, and R ⁷ and R ⁸ represent a methyl group, an ethyl group or a hydroxyethyl group). And 8% by weight of formula (IV):

[0014]

[Chemical 8]

(Wherein R ⁹ is an alkyl group having 1 to 4 carbon atoms, R ¹⁰ is an alkylene group having 1 to 2 carbon atoms, R ¹¹ and R
⁽¹² means hydrogen or a methyl group) 1 to 70% by weight of a glycol ether type solvent represented by the formula (1) to provide a liquid detergent composition for exclusive use of dipping and washing.

R ¹ and R ² in formula (I) may be the same or different and have 12 to 24 carbon atoms, preferably 16 carbon atoms.
To 20 straight or branched chain alkyl or alkenyl groups. When the carbon number is less than 12, the fabric after washing cannot be provided with sufficient flexibility and texture, and when the carbon number exceeds 24, it does not melt transparently at low temperature.

R ³ and R ^{4, which} may be the same or different, are a methyl group, an ethyl group or a polyoxyethylene group or a polyoxypropylene group, preferably a methyl group. The number of added moles of polyoxyethylene group or polyoxypropylene group is preferably 1 to 5, particularly preferably 1 to 3.

X is a halogen atom, CH ₃ SO ₄ or C ₂
H ₅ SO ₄ . Preferred is a halogen atom. Examples of the halogen atom include chlorine, bromine and iodine, and chlorine is preferable.

The cationic surfactant represented by the formula (I) is a quaternary ammonium salt, specifically, dioleyldimethylammonium chloride, a mixed unsaturated alkyl group derived from oleic acid or tallow fatty acid or soybean oil fatty acid. And dioleyldimethylammonium chloride are particularly preferable. The cationic surfactants may be used alone or as a mixture of two or more kinds, and the cationic surfactant used has an iodine value of 40 to 100, preferably 60 to 90.
Is. The system containing this cationic surfactant is transparent, but when the iodine value is less than 40, the cause thereof is not clear, but a cloudy precipitate is deposited at 0 to 10 ° C. The content of the cationic surfactant is 1 to 5% by weight in the composition.
If the amount is less than 1% by weight, the fibers after washing are not imparted with flexibility, and if the amount exceeds 5% by weight, cloudy precipitates are likely to be deposited at low temperature and the detergency is lowered, and recontamination is likely to occur.

R ⁵ in the formula (II) has 10 to 20 carbon atoms.
Alkyl group or alkenyl group, or having 6 carbon atoms
An alkylphenyl group having an alkyl group of
It is preferably an alkyl group or an alkenyl group. Therefore, the nonionic surfactant represented by the formula (II) has an addition mole number of ethylene oxide of 5 to 15, preferably 7 to
12 polyoxyethylene alkyl or alkenyl ether or 6 to 12, preferably 8 to 10 carbon atoms
Is a polyoxyethylene alkyl phenyl ether having an alkyl group of. The content of the nonionic surfactant in the composition is 10 to 30% by weight, preferably 15 to 25% by weight. If it is less than 10% by weight, the detergency is weak and re-contamination is likely to occur, and the stability at low temperature decreases. On the other hand, 30% by weight
If it exceeds, the solubility at room temperature tends to be poor and the gel tends to form.

R ⁶ in formula (III) has 10 to 2 carbon atoms.
2, preferably 12 to 18 straight chain or branched chain alkyl groups, and particularly preferably 12 to 14.

R ⁷ and R ⁸ are a methyl group, an ethyl group or a hydroxyethyl group, preferably a methyl group.

The semipolar surfactant represented by the formula (III) is added to improve the solubility, foaming power and detergency of the system, and its content is 0.5 to 8% by weight in the composition. , Preferably 1 to 7% by weight. If it is less than 0.5% by weight, the solubility of the system is poor and a film may be formed on the liquid surface over time, and if it exceeds 8% by weight, not only the defoaming becomes worse, but also -5 ° C.
The stability at is reduced.

In the formula (IV), R ⁹ is a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ¹⁰ is an alkylene group having 1 to 2 carbon atoms, preferably 2.

R ¹¹ and R ¹² are hydrogen or a methyl group. Specific examples of the glycol ether solvent represented by the formula (IV) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, and 3-methoxybutanol. , 3-methyl-3-methoxybutanol, etc., such as isopropylene glycol monomethyl ether, isopropylene glycol monoethyl ether, 3-methoxybutanol, and 3-methyl-3-methoxybutanol, which have 3 carbon atoms.
The above glycol ethers are preferred.

The glycol ether type solvent is added to improve the detergency at the time of leaving and washing, and its content in the composition is 1 to 70% by weight, preferably 5 to 50% by weight,
Particularly preferably, it is 8 to 30% by weight. If it is less than 1% by weight, no improvement in cleaning is observed.

In the present invention, the formulas (II) to (IV)
As for the above component, two or more kinds can be used in combination. Further, in the present invention, the weight of the total amount of the nonionic surfactant represented by the formula (II) and the semipolar surfactant represented by the formula (III) with respect to the cationic surfactant represented by the formula (I). The ratio is preferably 1:20 to 1: 4, more preferably 1:13 to 1: 5. At this time, if the compounding ratio of the cationic surfactant represented by the formula (I) is less than 1:20, the effect of imparting flexibility to the fiber is not exhibited, and conversely if it is more than 1: 4, the low temperature stability decreases. In addition, the detergency is reduced, and recontamination is likely to occur.

The composition of the present invention may contain a solubilizing agent such as ethylene glycol, propylene glycol, glycerin or ethanol in order to further improve the solubility. Further, a water-soluble polymer such as polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl methyl cellulose or hydroxybutyl cellulose may be blended in order to improve detergency or prevent recontamination. Further, for example, an enzyme such as a protein hydrolase, a lipid hydrolase, a starch hydrolase, a lytic enzyme, etc. can be added.

Further, the composition of the present invention may be appropriately blended with additives usually used for this type of detergent, such as perfumes, enzymes, bactericides, pigments and dyes.

The composition of the present invention can be produced by mixing and dissolving the desired components by a conventional method, and when used, the composition of the present invention is usually used in an amount of 200 to 2000 times the volume of water or warm water (10 to 10 times). 30 ° C), and after placing the article to be washed on it for a short time, for example, 10 to 30 minutes,
By just rinsing, stains can be removed without problems such as shrinkage of clothes, and the texture can be washed well. The composition of the present invention is particularly suitable for washing products such as silk and wool that require delicate washing.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples,% in concentration and amount used is% by weight. The stability test, flexibility test, shrinkage test and detergency test were conducted as follows. The water used in these tests was tap water, and the flexibility test, shrinkage test and detergency test were all examined by placing and washing as a standard, and the silk cloth used was a satin woven cloth of 100% silk from Tango. Is.

Stability Test A liquid detergent composition was prepared at about 70 ° C. and then cooled to about 40 ° C. This was placed in a 100 ml screw tube and left for 1 month in a constant temperature bath of -5 ° C, 0 ° C, 5 ° C and 25 ° C, and its appearance was visually evaluated. The evaluation criteria are as follows. ○ Transparent, with fluidity △ Semi-transparent, with fluidity × White turbidity, crystal precipitation or solidification

Flexibility test 10 cm of 20 cm × 20 cm silk cloth was placed in 500 ml of a 0.1% aqueous solution of a liquid detergent composition at 30 ° C.
After soaking for 2 minutes and shaking and rinsing twice, the pieces were dehydrated for 10 seconds and air-dried. This washing operation was set as one cycle and repeated for 5 cycles. After the completion of 5 cycles, a low temperature iron was applied to give a test cloth. This cloth was subjected to a pairwise comparison with an unwashed cloth by feeling by 8 judges, and judged as follows. The evaluation criteria are as follows. ◎ Much softer than unwashed silk cloth ○ Softer than unwashed silk cloth △ Slightly harder than unwashed silk cloth × Harder than unwashed silk cloth

Shrinkability Test (1) A raw silk cloth having a size of 30 cm × 30 cm was conditioned at 20 ° C. and 65% RH for 4 hours or more. Mark 8 points on this cloth with an oil-based felt-tip pen, number each, and then measure the length between each mark (vertical a ₁ ^O ,
a ₂ ^O , a ₃ ^O ; horizontal b ₁ ^O , b ₂ ^O , b ₃ ^O ), and this length was used as the original length to prepare a test cloth. FIG. 1 shows a plan view of the test cloth.

(2) The three test cloths obtained in (1) were put in one beaker (1 liter), and put on and washed. Each detergent concentration was 0.1%, and the water temperature was 20 ° C. 2 rinses in a beaker (1 liter)
I've done it. Then, this test cloth was attached to the wall of the dehydration tub of the washing machine, and after the rotation was stabilized, it was dehydrated for 10 seconds, then placed on a net and laid flat to dry, and then at 20 ° C and 65% RH for 4 hours or more. Humidified. Furthermore, the lengths between the marks marked in (1) above are measured again (vertical a ₁ ^w , a ₂ ^w , a ₃ ^w ; horizontal b ₁ ^w , b ₂ ^w , b ₃ ^w ), From this, the shrinkage rate was calculated according to the following formula.

[0036]

[Equation 1]

O. M. : Measured value before washing (original length) W. M. : Measured value after washing

Detergency test 10 cm × 1 in 500 ml of an aqueous solution of the detergent composition
Two 0 cm artificially contaminated cloths and two white cloths were dipped, adjusted to have a bath ratio of 1: 100, placed in a beaker and washed. The washing conditions and the composition of the artificially contaminated cloth are as follows.

<Cleaning conditions> Cleaning time: 20 minutes Cleaning composition: 0.1% Cleaning temperature: 20 ° C. Rinse: Shake rinse Rinse dehydration: 10 seconds after the rotation of the dehydration tank is stabilized

<Soil composition of artificially contaminated cloth (%)> Oleic acid 15.0 Palmitic acid 7.5 Myristic acid 7.5 Beef tallow oil 30.0 Cholesterol 10.0 Squalene 5.0 Cetyl alcohol 10.0 Paraffin 15.0

An artificial dirt was obtained by dispersing carbon black in the dirt composition. As for the cleaning rate and the redeposition rate, the reflectances of the artificially contaminated cloth before and after the cleaning, and the white cloth before and after the cleaning were measured with a color computer, and the cleaning rate and the redeposition rate were calculated by the following equations.

[0042]

[Equation 2]

[0043]

[Equation 3]

R ₀ : Surface reflectance of white cloth _RS : Surface reflectance of contaminated cloth R _w1 : Surface reflectance of contaminated cloth after cleaning R _w2 : Surface reflectance of white cloth after cleaning

Examples 1 to 6 and Comparative Examples 1 to 7 Liquid detergent compositions having the compositions shown in Tables 1 and 2 were produced according to a conventional method, and each composition was subjected to a stability test, a flexibility test and a shrinkability. Tests and detergency tests were conducted. The results are shown in Tables 1 and 2.

[0046]

[Table 1]

[0047]

[Table 2]

From these results, it is clear that the liquid detergent composition of the present invention is excellent in stability, flexibility, anti-shrinkage property and detergency. Regarding the detergency, if the difference in detergency is 5% or more, it can be clearly identified visually. As shown in Comparative Example 5, when the blending amount of the glycol ether solvent represented by the formula (IV) is less than 1.0%, the detergency is obviously poor. In addition, as shown in Comparative Examples 2, 3 and 4, the formula
When a solvent other than the glycol ether solvent represented by (IV) was used, the detergency was not sufficiently exhibited, and the gelation occurred in terms of stability.

[0049]

The liquid detergent composition of the present invention has a practical detergency and a shape retaining function when washing silk products, wool products, fashionable clothes, etc. A texture can be imparted, and the form as a liquid cleaning agent that is stable and transparent at room temperature and low temperature and that is dedicated to washing by placing can be retained.

[Brief description of drawings]

FIG. 1 is a plan view of a test cloth for shrinkage test.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C11D 3:20)

Claims (3)

[Claims] 1. Formula (I): (In the formula, R ¹ and R ² are alkyl groups or alkenyl groups having 12 to 24 carbon atoms, R ³ and R ⁴ are methyl groups, ethyl groups, polyoxyethylene groups or polyoxypropylene groups, X is a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO
₁ means or a mixture of two or more kinds selected from compounds represented by the formula (4), and 1 to 5% by weight of a cationic surfactant having an iodine value of 40 to 100, and a compound represented by the formula (II): ] (Wherein R ⁵ is an alkyl or alkenyl group having 10 to 20 carbon atoms, or an alkylphenyl group having an alkyl group having 6 to 12 carbon atoms, and n is 5 to 15). 10 to 30% by weight of the formula (III): (Wherein R ⁶ represents an alkyl group having 10 to 22 carbon atoms, R ⁷ and R ⁸ represent a methyl group, an ethyl group or a hydroxyethyl group), and a semipolar surfactant is 0.5 to 8% by weight. And formula (IV): (In the formula, R ⁹ represents an alkyl group having 1 to 4 carbon atoms, R ¹⁰ represents an alkylene group having 1 to 2 carbon atoms, and R ¹¹ and R ¹² represent hydrogen or a methyl group). A liquid detergent composition for exclusive use of soaking and placing, characterized in that the liquid detergent composition contains 70% by weight to 70% by weight. 2. The liquid detergent composition according to claim 1, wherein R ¹⁰ in the glycol ether solvent represented by the formula (IV) is an ethylene group. 3. The weight ratio of the total amount of the components of formulas (II) and (III) to the component of formula (I) is 1:20 to 1: 4.
The liquid detergent composition according to claim 1, which is