JPH0848995A - Liquid detergent composition - Google Patents

Abstract

PURPOSE:To improve storage stability at ordinary and low temps. and solubility for dilution with water by incorporating a specific cationic surfactant, a specific nonionic surfactant, a specific amine oxide, and a specific polyhydric alcohol. CONSTITUTION:A cationic surfactant (A) having an iodine value of 40-100 and represented by formula I (wherein R<1> and R<2> each is an alkyl or alkenyl; R<3> and R<4> each is methyl, ethyl, or a polyoxyethylene or polyoxypropylene group; and X is a halogen, CH3SO4, or C2H5SO4) is compounded in an amount of 1-5wt.% with 10-30wt.% nonionic surfactant (B) represented by formula II (wherein R<5> is a 10-20C alkyl or alkenyl or an alkylphenyl having a 6-12C alkyl and (n) is 5-15), 0.5-8wt.% amine oxide (C) represented by formula III [wherein R<6> is a 10-22C alkyl or (hydroxy)ethyl], and 1-70 wt.% polyhydric alcohol represented by formula IV (wherein R<9> is a 2-6C alkylene and (p) is 1-9) in such a proportion that the weight ratio of the ingredient (A) to the sum of the ingredients (B) and (C) is 1:(20-4).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a liquid detergent composition, in particular, a transparent liquid detergent composition for soaking, and more particularly, to clean even slight stains such as silk products, wool products and fashionable clothes. It has a practical cleaning power for clothes that need to be stored, and has storage stability at normal and low temperatures.
The present invention relates to a liquid detergent composition which is excellent in solubility when diluted in water and which is used for washing by leaving it in a pickle. Further, the composition can be used for removing stains such as oily stains in a thick state.

[0002]

2. Description of the Related Art Conventionally, pickling and placing washing generally refers to pre-washing before washing in a washing machine, hand washing (fir-washing), etc., or dipping it in a detergent solution containing an enzyme to enhance the washing power. I meant to put it. Therefore, silk and wool garments that have not been sufficiently cleaned unless soaked for a long time (for example, overnight) are
There were many problems that "clothes shrink". When such clothes are dry-cleaned, there is no problem of shrinkage, but problems such as "water-soluble stains are hard to remove" have occurred. Furthermore, in dry cleaning, "solvent causes environmental pollution", so we ask a cleaning shop
There are problems such as "poor economy" and "takes time".
There was a need to wash these clothes at home. JP-A-4-4298 and JP-A-4-153300 disclose a neutral transparent liquid which has a proper cleaning power in a one-pack type cleaning method, does not impair excellent texture, and has excellent storage stability. Detergents are listed. This one-pack type composition mainly comprises a nonionic surfactant or an amine oxide 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. Is. But silk products,
For wool products, fashionable clothes, etc., after washing with normal washing methods (specifically, washing with a mild water stream in a washing machine or washing by hand movements such as leaning, pushing, etc.) The clothing of the item shrinks or loses its shape, which significantly reduces the commercial value of the item. As a washing method for preventing the shrinkage and deformation of clothing, the soaking and washing method is known. However, the above-mentioned detergents have poor solubility (dispersibility) when diluted in water, resulting in reduced washing power and uneven washing. Cause of.

Further, in the soaking and washing method, it is not necessary to use a washing machine, and treatment with a wash basin or a tub is possible. In this case, however, the detergent must be dissolved in water by hand. However, if the solubility is poor, long-term stirring is required, which is complicated. Furthermore, the treatment of cold water such as winter requires pain in the hands. Therefore, it has practical cleaning power for silk products, wool products, fashionable clothes, etc., and has excellent storage stability at room temperature and low temperature, and excellent solubility (dispersibility) when diluted in water. A liquid detergent composition has been sought.

[0004]

The present invention has practical cleaning power for silk products, wool products, fashionable clothes, etc., storage stability at room temperature and low temperature, and solubility when diluted in water ( It is an object of the present invention to provide a liquid detergent composition which is excellent in dispersibility and is particularly suitable for pickling and washing.

[0005]

The present invention provides the formula (I):

[0006]

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(In the formula, R ¹ and R ² have 12 to 24 carbon atoms.
Is an alkyl or alkenyl group, R ³ and R ⁴ are methyl groups, ethyl groups, polyoxyethylene groups or polyoxypropylene groups, 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 compounds having an iodine value of 4
1-5% by weight of a cationic surfactant of 0-100 and formula (II):

[0008]

[Chemical 6]

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

[0010]

[Chemical 7]

0.5 to 8% by weight of an amine oxide represented by the formula (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 equation (IV):

[0012]

Embedded image

1 to 70% by weight of one or more polyhydric alcohols represented by the formula (wherein R ⁹ is an alkylene group having 2 to 6 carbon atoms and n is 1 to 9) The present invention provides a liquid detergent composition characterized by the above.

R ¹ and R ² in formula (I) may be the same or different and have 12 to 24 carbon atoms, preferably
It is a linear or branched alkyl group or alkenyl group of 16 to 20. 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 may be the same or different and are a methyl group, an ethyl group, a polyoxypropylene group or a polyoxyethylene group, preferably a methyl group. The addition mole number of the polyoxyethylene group or the polyoxypropylene group is preferably 1 to 5, particularly preferably 1 to
It is 3. X is a halogen atom, CH ₃ SO ₄ or C ₂ H ₅
SO ₄ , and preferably a halogen atom. Examples of the halogen atom include chlorine, bromine or iodine,
Chlorine is preferred.

The cationic surfactant represented by the formula (I) is a quaternary ammonium salt, specifically, dioleyldimethylammonium salt, mixed unsaturated alkyl derived from oleic acid or tallow fatty acid or soybean oil fatty acid. And dialkyldimethylammonium salt of the group. Particularly, dioleyl dimethyl ammonium salt is preferable. The cationic surfactants may be used singly or as a mixture of two or more kinds, and the iodine value of the whole cationic surfactant used is 40 to 100, preferably 60 to 90. The system containing this cationic surfactant is transparent, but when the iodine value is less than 40, the cause is not clear, but a cloudy precipitate is deposited at low temperature, which is not preferable. The content of the cationic surfactant is 1 to 5% by weight in the composition. If it is less than 1% by weight, the fibers after washing will not have flexibility, and
If it exceeds 5% by weight, a cloudy precipitate is likely to be deposited at low temperature and the detergency is lowered.

R ⁵ in the formula (II) has 10 to 20 carbon atoms.
An alkyl or alkenyl group having 6 to 1 carbon atoms
An alkylphenyl group having 2 alkyl groups, 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
~ 12 polyoxyethylene alkyl or alkenyl ether or C6 ~ 12, preferably 8 ~
Polyoxyethylene alkyl phenyl ethers having 10 alkyl groups are preferred. The content of the nonionic surfactant in the composition is 10 to 30% by weight, preferably 1%.
It is 5 to 25% by weight. If it is less than 10% by weight, the detergency is weak and the stability at low temperature is lowered. On the other hand, if it exceeds 30% by weight, the solubility at room temperature is poor and the gel tends to be formed.

R ⁶ in the formula (III) has 10 to 2 carbon atoms.
2, preferably 12 to 18 linear or branched alkyl, particularly preferably 12 to 14. R
⁷ and R ⁸ are a methyl group, an ethyl group or a hydroxyethyl group, and preferably a methyl group. Formula (III)
Is added to improve the stability, foaming power and detergency of the composition, and the content thereof is 0.5 to 8% by weight, preferably 1 to 7% by weight in the composition.
Is. If it is less than 0.5% by weight, the solubility of the composition is poor,
A film may be formed on the liquid surface over time, and if it exceeds 8% by weight, not only the foam breakage becomes worse, but also the storage stability at -5 ° C decreases.

In the formula (IV), R ⁹ is a linear or branched alkylene group having 2 to 6 carbon atoms, preferably 3 to 6 carbon atoms. n is 1 to 9, preferably 1 to 3. Specific examples of the polyhydric alcohol represented by the formula (IV) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and P.
EG 200, PEG 300, PEG 400, propylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, hexylene glycol, etc. And preferably propylene glycol,
Dipropylene glycol, 1,3-butanediol, 2,
3-butanediol, 1,4-butanediol, 1,5-pentanediol and hexylene glycol are preferable, and 1,5-pentanediol and hexylene glycol are particularly preferable. Specific examples of the solvent not included in the polyhydric alcohol represented by the formula (IV) include polyethylene glycol having an average molecular weight of 600 or more and trivalent or more alcohols such as glycerin and sorbit. The polyhydric alcohol is added to improve the solubility when diluted in water, and its content in the composition is 1 to 70% by weight, preferably 5 to 50% by weight, and more preferably,
It is 10 to 50% by weight. If it is less than 1% by weight, improvement in solubility upon dilution with water and stability at low temperature are not observed. Further, if it exceeds 70% by weight, the stability at room temperature and low temperature is not recognized.

In the present invention, each of the components of formulas (II) to (IV) may be used in combination of two or more kinds. Further, in the present invention, the weight ratio of the total amount of the nonionic surfactant represented by formula (II) and the amine oxide represented by formula (III) to the cationic surfactant represented by formula (I) is 1 : 20 to 1: 4 is preferable, and 1:13 to 1: 5 is more preferable. At this time, when 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, when it is more than 1: 4, the low temperature stability becomes low. And also the detergency.

The composition of the present invention can be produced by mixing and dissolving the desired components by a conventional method, and further, in order to improve detergency or prevent redeposition, polyvinyl polyhydric alcohol, carboxymethyl. Water-soluble polymers such as cellulose, hydroxypropylmethyl cellulose and hydroxybutyl cellulose can be added. 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 can be appropriately blended with additives usually used for this type of detergent, such as fragrances, bactericides, pigments and dyes.

In using the composition of the present invention,
200 to 2000 times the volume of the composition or hot water (1
(0 to 30 ° C), and by soaking the item to be washed in it for a short time, for example, for 10 to 30 minutes, and then rinsing it, it is possible to remove stains without problems such as shrinkage of clothes and feel. 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. Furthermore, the composition of the present invention in the state of undiluted solution,
When used in the same manner as a conventional stain remover, it can be suitably used as a stain remover for oily stains.

[0022]

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. A stability test, a solubility (dispersibility in water) test and a detergency test were conducted as follows. The water used for these tests was tap water, and the detergency test was conducted by dipping and washing.

Stability Test A liquid detergent composition is prepared by stirring and mixing at about 60 ° C and cooling to about 40 ° C. This was placed in a 100 ml screw tube and left in a constant temperature bath at -5 ° C and 25 ° C for 1 month to visually determine the appearance. In addition, the viscometer
The viscosity was measured by a BM type viscometer manufactured by Tokimec), and this judgment was also evaluated. The evaluation criteria are as follows. ◎ Transparent, fluid, viscosity less than 2000 cps ○ Semi-transparent, fluid, viscosity less than 2000 cps × gelling, cloudy, separated, viscosity 2000 cps or more

Flexibility test 500 ml of 0.1% aqueous solution of liquid detergent composition at 30 ° C.
A 20 cm × 20 cm silk cloth was immersed in the solution for 10 minutes, and after rinsing by shaking twice with new water, it was dehydrated by towel drying and air-dried. 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. 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. ○ Softer than unwashed silk × Harder than unwashed silk

Dispersibility test-1: Solubility test when diluted in water A beaker containing 1 liter of tap water (20 ° C.) was stirred at a constant speed, and 1 g of a detergent composition measured by a syringe was added to complete the test. The time until dissolution in was measured. The evaluation criteria are as follows. ◎ Less than 20 seconds ○ 20 seconds or more and less than 40 seconds × 40 seconds or more

Detergency Test-1 5 sheets of 5 cm × 5 cm artificially contaminated cloth (wet artificially contaminated cloth manufactured by Japan Society for Laundry Science) were immersed in 1 liter of an aqueous solution of a cleaning composition,
It was immersed in the beaker and washed. The washing conditions are as follows. <Washing conditions> Washing time: 20 minutes Washing temperature: 20 ° C Detergent concentration: 0.1% Rinse: Shake rinse Rinse dehydration: Towel dry Dry: Iron <Soil components of artificially contaminated cloth> Oleic acid 28.3% Triolein 15.6% Cholesterol oleate 12.2% Liquid paraffin 2.5% Squalene 2.5% Cholesterol 1.6% Gelatin 7.0% Mud 29.8% Carbon black 0.5% The reflectance before and after washing was measured with a color computer (color difference meter model ND-1001DP manufactured by Nippon Denshoku Industries Co., Ltd.) and calculated by the following formula.

[0027]

[Equation 1] The symbols in the formula represent the following numerical values. R0: Surface reflectance of white cloth Rs: Surface reflectance of contaminated cloth Rw: Surface reflectance of contaminated cloth after washing

Dispersibility test-2: Dispersibility test when diluted with water 25 cm × 3 containing 1 liter of tap water (20 ° C.) shown in FIG.
In a 0 cm tray, 1 g of the detergent composition measured with a syringe was added to the position of, and the position of was stirred with a stirrer for 20 seconds, left for 10 minutes, and the detergent solution was collected from the position of Was measured by a quantification method of a cationic surfactant (JIS K3362-5.4.3.). Further, the numerical value of the actually measured concentration when the theoretical concentration (0.1%) is set to 100 is shown.

Detergency test-2 A detergency test was conducted at the detergent concentration obtained in the dispersibility test-2. The conditions other than the detergent concentration were the same as those in the detergency test-1.

Comprehensive Evaluation A comprehensive evaluation was performed based on the results of the performance evaluation of each cleaning composition. The evaluation criteria are as follows for each of Table 1 and Table 3. Evaluation criteria in Table 1 ⊚: A composition in which all the results of the stability test (normal temperature and low temperature), the flexibility test and the dispersibility test-1 are ◎ and the results of the detergency test-1 are 17 or more. : Stability test (normal temperature and low temperature), one of the results of the flexibility test and the dispersibility test-1 is ◯, and the other is ◎,
And, a composition in which the result of the detergency test-1 is 17 or more x: a composition in which one or more of the results of the stability test (normal temperature and low temperature), the flexibility test and the dispersibility test-1 are x Evaluation criteria ◎: Stability test (normal temperature and low temperature) and dispersibility test-
Composition in which all the results of 1 are ⊚: Stability test (normal temperature and low temperature) and dispersibility test-
A composition in which one or two of the results of 1 are ◯ and all of the others are ⊚ x: stability test (normal temperature and low temperature), dispersibility test-1

Examples 1 to 9 and Comparative Examples 1 to 10 Liquid detergent compositions having the compositions shown in Table 1, Table 2 and Table 3 were produced according to a conventional method, and various tests and evaluations were carried out. First, the composition and the amount of the polyhydric alcohol represented by the formula (IV) were fixed, and the respective compositions in which the type and the compounded amount of the compounds represented by the formulas (I) to (III) were changed were prepared. Stability test, flexibility test, detergency test of each composition-
1 and dispersibility test-1 were evaluated, and a comprehensive evaluation was performed. The results are summarized in Table 1.

[0032]

[Table 1]

As a result, when the iodine value of the cationic surfactant represented by the formula (I) in Comparative Example 1 is out of the range of 40 to 100, the cationic interface represented by the formula (I) in Comparative Examples 2 and 3 is used. The amount of the activator compounded in the composition is 1
When it is out of the range of 5% by weight, the compounding amount of the nonionic surfactant represented by the formula (II) in Comparative Examples 4 and 5 is 10
When it is outside the range of 30% by weight, and the formula in Comparative Example 6
When the compounding amount of the amine oxide represented by (III) is out of the range of 0.5 to 8% by weight, the stability and the flexibility are lowered.

Next, in order to demonstrate that if the detergent composition has poor solubility in water, it causes a decrease in washing power and uneven washing, and therefore, the compounds represented by the formulas (I) to (III) are used. Evaluation of dispersibility test-1 and 2 and detergency test-2 of each composition when the type and amount of the polyhydric alcohol represented by the formula (IV) are changed while the type and amount are fixed. went. The results are shown in Table 2.

[0035]

[Table 2]

As a result, the dispersibility test-1 shows that the composition having a better solubility when diluted in water has a smaller cleaning power difference (cleaning unevenness) from the cleaning power test-2. Therefore, it is shown that the dispersibility test-1 is an index for evaluating the detergency test-2 (cleaning unevenness).

Next, the type and blending amount of the compounds represented by formula (I), formula (II) and formula (III) are fixed, and the type and blending amount of the polyhydric alcohol represented by formula (IV) are changed. Stability test and dispersibility test-1 of each cleaning composition
Was evaluated and comprehensive evaluation was performed. The results are summarized in Table 3.

[0038]

[Table 3]

As shown in Examples 6, 4, 1, 7, 8, 5 and 9 and Comparative Examples 7 to 12, when the polyhydric alcohol represented by the formula (IV) was not blended, dilution with water was performed. The solubility (dispersibility) at that time was poor, and the stability at room temperature and low temperature decreased.

From these results, the liquid detergent composition of the present invention is superior to the compositions of Comparative Examples in storage stability, detergency and solubility (dispersibility) when diluted with water. It is clear.

Example 9 The following components are heated and stirred at 60 ° C. to homogenize them. This was cooled with stirring to produce a liquid cleaning composition. Blending ingredients Blending amount (% by weight) Dioleyldimethylammonium chloride 4.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 23.0 Lauryl dimethylamine oxide 2.0 Hexylene glycol 10.0 Citric acid Sodium 0.2 Citric acid 0.05 Preservative 0.05 Perfume 0.5 Purified water 60.2

Example 10 The following components are heated and stirred at 60 ° C. to homogenize them. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Ingredient (wt%) Dioleyldimethylammonium chloride 1.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 15.0 Lauryl dimethylamine oxide 1.0 Hexylene glycol 50.0 Preservative 0.05 Purified water 32.95

Example 11 The following ingredients are heated to 60 ° C. and stirred to homogenize them. This was cooled with stirring to produce a liquid cleaning composition. Blending ingredients Blending amount (% by weight) Dioleyldimethylammonium chloride 4.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 18.0 Lauryl dimethylamine oxide 7.0 1,5-pentanediol 5. 0 Hexylene glycol 5.0 Sodium citrate 0.2 Citric acid 0.05 Preservatives 0.05 Perfume 0.5 Purified water 60.2

Example 12 The following components are heated and stirred at 60 ° C. to homogenize them. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Ingredient (wt%) Dioleyldimethylammonium chloride 5.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 20.0 Lauryl dimethylamine oxide 4.0 Hexylene glycol 20.0 Preservative 0.05 Perfume 0.5 Dye 0.1 Purified water 50.35

[0045]

EFFECTS OF THE INVENTION According to the present invention, when cleaning silk products, wool products, fashionable clothes, etc., it has a practical cleaning power, is stable at room temperature and low temperature, and has excellent solubility when diluted with water. A liquid detergent composition for soaking and washing is obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a test tray used for a dispersibility test of a cleaning composition.

[Explanation of symbols]: A point where the cleaning composition is added to the water in the tray, a point where stirring is performed with a stirrer, and a point where the concentration of the cleaning composition is measured,

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Claims (4)

[Claims] 1. Formula (I): (In the formula, R ¹ and R ² are alkyl 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 ₄
Which means 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 alkylphenyl group having an alkyl or alkenyl group having 10 to 20 carbon atoms or an alkyl group having 6 to 12 carbon atoms, and n is 5 to 15). 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 0.5 to 8% by weight of an amine oxide represented by the formula: (IV): (In the formula, R ⁹ is an alkylene group having 2 to 6 carbon atoms, and n is 1 to
(Meaning 9), and 1 to 70% by weight of one or more polyhydric alcohols. 2. The liquid detergent composition according to claim 1, wherein 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. . 3. The method according to claim 1, which is for pickling and leaving washing.
The liquid detergent composition described. 4. The liquid detergent composition according to claim 1, which is for removing stains.