JPH07242897A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To obtain a liquid detergent composition which comprises a specific nonionic surfactant, a cationic surfactant of a certain iodine value and a water- soluble silicone derivative, thus is excellent in cleaning power, shape retention, foam separation without damage to fabric hand. CONSTITUTION:This detergent composition comprises (A) 10 to 50wt.% of a nonionic surfactant of formula I (R<1> is a 10-22C alkyl, alkenyl; (n) is 5-15; (m) is 1-5); (B) 1 to 15wt.% of a cationic surfactant having 40 to 100 iodine value and the chemical structure represented by formula II (R<2>, R<3> are each a 12-24C alkyl, alkenyl; R<4>, R<5> are each methyl, ethyl, the formula: (CH2CH2O)pH ((p) is 1-15); X is a halogen, CH3SO4, CH3CH2SO4), and (C) 0.1 to 5wt.% of a water- soluble silicone derivative where the weight ratio of the component A to components B+C is 10/2 to 2/1. The product always shows an appropriate level of detergency and shape retention with clear foam separation, when fashion clothes made of silk or wool must be washed even due to a slight bit of stain.

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 exclusively for putting on, and more particularly, it is suitable for clothes such as silk products, wool products, and fashionable clothes which require cleaning even with slight dirt. Has detergency and shape retention function,
The present invention relates to a liquid detergent having good defoaming properties, excellent texture, and excellent storage stability.

[0002]

2. Description of the Related Art Generally, conventional soaking washing is a washing machine,
The term refers to pre-washing before washing by hand washing (rubbing), etc., or to attach it to a detergent solution that has been formulated with an enzyme to enhance the washing power. In this cleaning method, it is necessary to wear clothes for a long time (for example, overnight) in order to sufficiently remove dirt.

Conventionally, for washing clothes at home, after washing with a detergent containing an anionic surfactant or a nonionic surfactant as a main component, the texture and antistatic ability of the fiber are imparted. In addition, softening treatment is performed with a softening agent containing a cationic surfactant as a main component. However, this method requires two operations of washing and imparting flexibility, which is complicated. Therefore, Japanese Patent Publication No. 4750/1972 and Japanese Patent Publication No. 126896/1982 discuss a one-pack type cleaning composition in which the above operations are simultaneously performed. This one-pack type detergent composition is mainly composed of a nonionic surfactant or a semipolar surfactant, and has a monoalkyl type or dialkyl type cationic surfactant having a long-chain saturated alkyl group in the molecule. Is blended as a softening agent component. Further, in JP-A-4-4298, unsaturated dialkyl type cationic surfactants, polyoxyethylene alkyl ether type nonionic surfactants, and amine oxide type nonionic surfactants are used for the purpose of improving the texture after washing. A detergent composition in which agents are combined is proposed.

[0004]

Delicate clothes such as silk and wool need to be washed even in a slightly soiled state, but it takes a long time to wash them by the conventional soaking and washing. There was a problem of shrinking clothes. Further, the conventional detergent composition for soaking and placing is also disadvantageous in that foaming is poor at the time of rinsing because it contains a polyoxyethylene alkyl ether type nonionic surfactant as a main component. Further, the conventional one-pack type detergent composition has poor storage stability, and when stored for a long period of time, white turbidity or precipitation occurs at a low temperature, resulting in a drawback that the appearance of the composition is impaired.

The present invention has an appropriate cleaning power for removing stains from delicate garments by washing it for a short period of time and a shape-retaining function without shrinkage, has good defoaming, does not impair excellent texture, and The present invention provides a liquid detergent composition having excellent storage stability.

[0006]

[Means for Solving the Problems] As a result of repeated research to solve the above problems, a specific nonionic surfactant, a cationic surfactant having an iodine value in a specific range, and a water-soluble silicone are found. By combining the derivatives in a specific weight ratio, it has been possible to obtain a liquid detergent composition having a characteristic that has never been obtained. That is, the present invention provides the following a, b, c
, A is 10 to 50% by weight, b is 1 to 15% by weight, and c is
0.1 to 5% by weight, and the weight ratio of a to b + c is 10/1 to
The liquid detergent composition is 2/1. a. A nonionic surfactant represented by the formula (1).

[0007]

[Chemical 3]

(Wherein R ¹ is an alkyl or alkenyl group having 10 to 22 carbon atoms, n is 5 to 15 and m is 1 to 5) b. The iodine value represented by the formula (2) is 40 to 100 cationic surfactants.

[0009]

[Chemical 4]

(Wherein R ² and R ³ are alkyl or alkenyl groups having 12 to 24 carbon atoms, R ⁴ and R ⁵ are methyl groups,
Ethyl or _{- (CH 2 CH 2 O)} p is 1 to 15 as _P H, X
Represents a halogen atom, CH ₃ SO ₄ , or C ₂ H ₅ SO ₄ ) c. Water-soluble silicone derivative. In the nonionic surfactant represented by the formula (1), R ¹ is an alkyl group or an alkenyl group having 10 to 22 carbon atoms, and for example, lauryl group, myristyl group, palmityl group, stearyl group, oleyl group, coconut oil alkyl Group, beef tallow alkyl group, etc., and if the carbon number is 9 or less, the texture is impaired,
When it is 23 or more, the storage stability becomes poor. n is 5 to 15,
The average addition mole number of ethylene oxide is shown. When n is less than 5, storage stability becomes poor, and when it exceeds 15, foam breakage at the time of rinsing becomes poor. m is 1 to 5 and represents the average number of moles of propylene oxide added. When m is less than 1, foam breakage at the time of rinsing becomes poor and the texture is impaired, and when it exceeds 5, storage stability becomes poor. Ethylene oxide and propylene oxide are block additions, respectively, and the random addition impairs the feel, and if the order of addition of ethylene oxide and propylene oxide is reversed, the storage stability deteriorates.

In the cationic surfactant represented by the formula (2), R ² and R ³ are alkyl groups or alkenyl groups having 12 to 24 carbon atoms, for example, lauryl group, myristyl group, palmityl group, stearyl group, Examples thereof include a behenyl group, an oleyl group, a coconut oil alkyl group, and a beef tallow alkyl group. When the carbon number is 11 or less, the texture is impaired, and when the carbon number is 25 or more, the storage stability is deteriorated. R ⁴ and R ⁵ are a methyl group, an ethyl group, or - with _{(CH 2 CH 2 O) p} H, p is 1 to 15, it represents an average addition mole number of ethylene oxide, texture when p is more than 15 Be damaged. X is a halogen atom, CH ₃ SO ₄ ,
Alternatively, it represents C ₂ H ₅ SO _4, and examples of the halogen atom include chlorine, bromine, and iodine. This cationic surfactant has an iodine value of 40 to 100. When the iodine value is less than 40, the shape retention function and texture are impaired, and when it exceeds 100, the defoaming during rinsing becomes poor.

Examples of the water-soluble silicone derivative of the component c include polyether modified silicone derivative, alcohol modified silicone derivative, amino modified silicone derivative, epoxy modified silicone derivative, carboxyl modified silicone derivative and the like. a is 10 to 50% by weight, but 10
If it is less than 50% by weight, the detergency and storage stability will be reduced,
If it exceeds, the defoaming will be worse.

The content of b is 1 to 15% by weight, but if it is less than 1% by weight, the shape retention function and texture are impaired, and if it exceeds 15% by weight, the detergency and storage stability are deteriorated. Although c is 0.1 to 5% by weight, when it is less than 0.1% by weight, the shape retention function and texture are impaired and foam breakage deteriorates, and when it exceeds 5% by weight, the detergency and storage stability decrease. The weight ratio of a and b + c is 10 /
Although it is 1 to 2/1, when a is larger than this, the shape-retaining function and texture are impaired and foam breakage is worsened, and when it is smaller, detergency and storage stability are deteriorated.

The detergent composition of the present invention contains components which are generally incorporated as desired, for example, solubilizing agents such as glycerin, ethylene glycol, propylene glycol, polyethylene glycol and ethanol, polyvinyl alcohol,
Builders such as carboxymethylcellulose, hydroxypropylmethylcellulose, hydroxybutylcellulose, sodium silicate, sodium carbonate, sodium aluminosilicate, sodium tripolyphosphate, etc., bactericides such as paraoxybenzoate, phenoxyethanol, benzalkonium chloride, didecyldimethylammonium chloride. , Ethylenediaminetetraacetic acid derivatives, citric acid, chelating agents such as trisodium nitrilotriacetic acid, UV absorbers such as benzophenone derivatives and benzotriazole derivatives, and other dyes, fragrances and the like may be contained to the extent that the effects of the present invention are not impaired. .

[0015]

EXAMPLES The present invention will be specifically described with reference to examples. The test methods and evaluation methods used in the examples are shown below. The water used for these tests is tap water. The texture test, the shape retention test, the detergency test, and the foam breaking test were all conducted on the basis of placing and washing, and the silk cloth used was a satin woven cloth made of 100% silk from Tango.

(1) Storage stability A liquid detergent composition was prepared at about 70 ° C and then cooled to about 40 ° C. Transfer this to a 100 ml screw tube and store at -5 ° C and 2
The sample was allowed to stand in a constant temperature bath at 5 ° C for 1 month, and the change in its appearance was visually evaluated, and evaluated according to the following three grades. ◯: Good storage stability (transparent dissolution state, fluidity) Δ: Slightly poor stability (some turbidity, fluidity) ×: Poor stability (separation, precipitation observed, or solidification)

(2) Texture A 500 ml aqueous solution of the liquid detergent composition having a concentration of 0.1% by weight was placed in a beaker of 1 liter, and a 20 cm × 20 cm silk cloth was dipped in the beaker for 10 minutes and rinsed twice. Then, it was dehydrated and dried for 10 seconds. This washing operation was defined 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. Twenty women were panelists and a pair of comparisons were made between this cloth and the unwashed cloth due to the feeling of touch. 3 points if the test cloth feels much softer than unwashed, 2 points if the test cloth feels somewhat soft,
The average value of 20 persons was calculated with 1 point when feeling slightly hard and 0 point when feeling very hard, and evaluated in the following 3 grades. Good texture (average value of 2.5 points or more) Slight texture (average value of less than 2.5 points and 1.5 points or more) Weak texture (average value of less than 1.5 points)

(3) Shape retention The unprocessed silk cloth with a size of 30 cm × 30 cm is kept at 20 ° C. and 65%.
The humidity was adjusted to RH for 4 hours or more. Mark the eight locations in oily felt pen on the fabric (4 corners and the center of each side of the fabric), then numbered respectively, to measure the length between the respective sign (vertical a ₁ ^0, a ₂ ⁰ , a ₃ ⁰ ; horizontal b ₁ ⁰ , b ₂ ⁰ ,
b ₃ ^0), it was the length of the original length. The three test cloths obtained in 1. were placed in one beaker of 1 liter and washed by putting them on. The concentration of the liquid detergent composition was 0.1% by weight, and the water temperature was 20 ° C. As rinsing, shaking rinsing was performed twice in a 1 liter beaker. Then, attach this test cloth to the wall of the dehydration tub of the washing machine, dehydrate for 10 seconds after the rotation is stabilized, lay it on a net and dry it flatly at 20 ° C, 65% RH for 4 hours or more. Humidified. Further, the length between them is measured again for the marks marked in (vertical a ₁ ^W , a ₂ ^W , a ₃ ^W ; horizontal b
₁ ^W , b ₂ ^W , b ₃ ^W ), and the shrinkage rate of the test cloth was calculated from the following formula.

[0019]

[Equation 1]

O. M. : Original length of the test cloth (vertical a ₁ ^0, a
₂ ^0, a ₃ ^0; lateral ^{_{b 1 0, b 2 0,}} b 3 0) W. M. : Length after cleaning (vertical a ₁ ^W , a ₂ ^W , a ₃ ^W ; horizontal b ₁ ^W , b ₂ ^W , b ₃ ^W ) The shrinkage rate calculated from each of three vertical and horizontal points is averaged, and The shape retention was evaluated from the average value in the following three stages. High form retention (vertical / horizontal shrinkage of less than 5.0%) Moderate shape retention (vertical / horizontal shrinkage of 5.0% or more 1
Less than 0.0%) Low shape retention (Shrinkage rate of vertical and horizontal is 10.0% or more)

(4) Detergency: 500 ml of the aqueous solution of the liquid detergent composition was placed in a 1 liter beaker, and two 10 cm × 10 cm artificially contaminated cloths and two white cloths were immersed in the beaker so that the bath ratio became 1: 100. It was adjusted to, and put on and washed. The washing conditions and the composition of the artificially contaminated cloth are as follows. <Washing conditions> Washing time 20 minutes Detergent composition concentration 0.1% by weight Washing temperature 20 ° C Rinse Shake Rinse Dewatering 10 seconds after the spin of the dehydration tank stabilizes <Soil composition of artificially contaminated cloth> Oleic acid 15.0 Palmitic acid 7.5 Myristic acid 7.5 Hardened beef tallow oil 30.0 Cholesterol 10.0 Squalene 5.0 Cetyl alcohol 10.0 Paraffin 15.0 What was made to disperse carbon black in this was made into artificial dirt, and the white cloth was contaminated with this and it was made into the artificial pollution cloth. After drying the contaminated cloth, color computer (Suga Test Instruments Co., Ltd.)
Measure the surface reflectance with, calculate the cleaning power from the following formula,
The following three grades were used for the evaluation.

[0022]

[Equation 2]

Excessive detergency (detergency of 25% or more) Detergency is good (detergency of 15% or more and less than 25%) Detergency is weak (detergency of less than 15%)

(5) Defoamability 500 ml of a 0.1% by weight aqueous solution of the liquid detergent composition was placed in a beaker of 1 liter, and a 20 cm × 20 cm silk cloth was immersed in this for 10 minutes, and rinsed twice. . Twenty women were panelists, and this cloth was tested by touch feeling. If you feel slimy to the touch and bubbles on your hands, 0
The average value of 20 persons was calculated by scoring 1 point when it was felt to be slightly slimy and 2 points when it was felt that it was not almost slimy, and evaluated in the following 3 grades. Good defoaming (average value of 1.5 points or more) Slightly bad defoaming (average value of 1.0 points or more and less than 1.5 points) Poor foam breaking (average value of less than 1.0 points)

Examples 1 to 10 and Comparative Examples 1 to 10 Samples having the formulations shown in Tables 1 to 4 were prepared and their performances were evaluated. The results are shown in Tables 1 to 4. The unit in the table indicates% by weight.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

In Tables 1 to 4, (Note 1) in the formula (1), R ¹ is 13, n is 8.5, and m is 2. (Note 2) In the formula (1), R ¹ is 13, n is 8.5, and m is 0. (Note 3) "Arcade 20-75I" manufactured by Lion Corporation (the main components are compounds of formula (2) in which R ² and R ³ are oleyl groups, R ⁴ and R ⁵ are methyl groups, and X is a chlorine atom, Iodine value is 70). "
It was used. (Note 4) "Nissan Cation 2-OLR" manufactured by NOF CORPORATION
(The main components are R ² and R ³ of the formula (2) are oleyl groups, R ⁴ and R ⁵
Is a methyl group, X is a chlorine atom, and the iodine value is
50) ”was used. (Note 5) "KF-351A (polyether-modified silicone)" manufactured by Shin-Etsu Chemical Co., Ltd. was used. (Note 6) "KF-393 (amino-modified silicone)" manufactured by Shin-Etsu Chemical Co., Ltd. was used.

From Tables 1 to 4, the compositions of Examples 1 to 10 of the present invention have an appropriate detergency to remove stains and a shape-retaining function without shrinkage when left standing and washing for a short time. well,
It is clear that the composition is a composition which does not impair the excellent texture and has excellent storage stability. The composition of Comparative Example 1 has a
Since it is less than 10% by weight, storage stability is poor and detergency is weak. In the composition of Comparative Example 2, since the content of a exceeds 50% by weight, the defoaming is poor. In the composition of Comparative Example 3, b is less than 1% by weight, so that the texture is poor and the shape retention is low. Comparative Example 4
In the composition (1), b is more than 15% by weight, the storage stability is poor and the detergency is weak. Since the composition of Comparative Example 5 had c of less than 0.1% by weight, the texture was poor and the shape retention was low.
The bubbles are not dry. In the composition of Comparative Example 6, c is more than 5% by weight, so that the storage stability is poor and the detergency is weak. Comparative Example 7
The composition (1) has a weight ratio of a to b + c of more than 10/1 and thus has poor texture, low shape retention, and poor foam breakage. Since the composition of Comparative Example 8 has a weight ratio of a to b + c of less than 2/1, it has poor storage stability and poor detergency. Since the composition of Comparative Example 9 uses the nonionic surfactant having m of formula (1) of 0, the shape retention is low and the defoaming is poor. Comparative Example 10
The composition (1) uses lauryldimethylamine oxide in place of (a), and therefore has poor storage stability, poor foam breakage, low shape retention, and poor detergency.

[0032]

EFFECT OF THE INVENTION The liquid detergent composition of the present invention has an appropriate detergency that stains can be removed by short-time standing and washing and a shape-retaining function without shrinkage, has good defoaming and impairs excellent texture. Since it is a liquid detergent composition that does not exist and has excellent storage stability, it is optimal for washing delicate clothes such as silk products, wool products, and fashionable clothes that require cleaning even with slight stains.

Claims (1)

[Claims] 1. The following a, b and c are contained, a is 10 to 50% by weight, b is 1 to 15% by weight and c is 0.1 to 5% by weight,
A liquid detergent composition, wherein the weight ratio of a to b + c is 10/1 to 2/1. a. A nonionic surfactant represented by the formula (1). [Chemical 1] (In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 to 22 carbon atoms, n represents 5 to 15 and m represents 1 to 5) b. A cationic surfactant represented by the formula (2) having an iodine value of 40 to 100. [Chemical 2] (In the formula, R ² and R ³ are alkyl groups or alkenyl groups having 12 to 24 carbon atoms, R ⁴ and R ⁵ are methyl groups, ethyl groups or — (CH ₂ CH ₂ O) _PH and p is 1 to 15, X represents a halogen atom, CH ₃ SO ₄ , or C ₂ H ₅ SO ₄ ) c. Water-soluble silicone derivative.