JP3124684B2 - Liquid detergent composition - Google Patents

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, in particular, a transparent liquid detergent composition for pickling, and more particularly to a method for cleaning even small stains such as silk products, wool products and fashionable clothes. It has practical detergency for clothing that needs to be stored, storage stability at room temperature and low temperature,
The present invention relates to a liquid detergent composition having excellent solubility upon dilution with water and for immersion washing. In addition, the composition can be used for removing stains such as oily stains in a concentrated state.

[0002]

2. Description of the Related Art Conventionally, immersion washing generally refers to prewashing before washing in a washing machine, hand washing (fir washing), etc., or immersing in a detergent solution containing an enzyme to enhance washing power. Was meant to be placed. Therefore, silk or wool garments, which have not been sufficiently stained unless soaked for a long time (for example, overnight), often have a problem of "shrinkage of clothing" due to long-term immersion. When such clothing is dry-cleaned, there is no problem of shrinkage, but problems such as "water-soluble stains are hardly removed" have been encountered. Furthermore, in dry cleaning, "solvents cause environmental pollution"
There are problems such as "poor economy" and "it takes time"
The need to wash these clothing at home has arisen. JP-A-4-4298 and JP-A-4-153300 disclose a neutral transparent liquid which has a proper detergency by a one-pack type cleaning method, does not impair an excellent texture, and has excellent storage stability. A cleaning agent is described. This one-pack type composition mainly contains a nonionic surfactant or an amine oxide as a main component, and contains a monoalkyl or dialkyl type cationic surfactant having a long-chain saturated group in a molecule as a softener component. It is. But silk products,
In the case of wool products, fashionable clothes, etc., after washing with the usual washing method (specifically, washing with a mild stream of water in a washing machine, washing with a hand movement by pushing or pushing) Garments shrink or lose their shape, significantly lowering the commercial value of the garments. As a washing method for preventing the shrinkage and shape loss of clothing, a pickling washing method is known. However, the above-mentioned detergent has poor solubility (dispersibility) upon dilution with water, resulting in reduced washing power, uneven washing, and the like. Cause.

[0003] In addition, the pickling washing method does not require the use of a washing machine, and can be treated with a basin or a tub, but in this case, the dissolution of the detergent in water must be performed manually. If the solubility is poor, stirring for a long time is required, which is complicated. Furthermore, the treatment in cold water, such as winter, is painful to the hands. Therefore, it has a practical detergency for silk products, wool products, fashionable clothes, etc., and has excellent storage stability at normal and low temperatures, and excellent solubility (dispersibility) when diluted with water for immersion washing. There has been a need for a liquid cleaning composition.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a practical detergency for silk products, wool products, fashionable clothes, etc., storage stability at ordinary and low temperatures, and solubility upon dilution with 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 immersion washing.

[0005]

The present invention provides a compound of the formula (I):

[0006]

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(Wherein R ¹ and R ^{2 each} have 12 to 24 carbon atoms)
An alkyl or alkenyl group, R ³ and R ⁴ are a methyl group, an ethyl group, a polyoxyethylene group or a polyoxypropylene group, and X represents a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO ₄ ) 1 to 5% by weight of a cationic surfactant having an iodine value of 40 to 100, which is one kind or a mixture of two or more kinds selected from the compounds represented by formula (II):

[0008]

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Wherein R ⁵ represents 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 represents 5 to 15; Activator 10-30% by weight
And formula (III):

[0010]

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Wherein R ⁶ represents an alkyl group having 10 to 22 carbon atoms, and R ⁷ and R ^{8 each} represent a methyl group, an ethyl group or a hydroxyethyl group. And formula (IV):

[0012]

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(Wherein R ⁹ represents an alkylene group having 2 to 3 carbon atoms, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, and n represents 2 to 3) The present invention provides a liquid detergent composition containing 1 to 70% by weight of a glycol ether.

R ¹ and R ² in the formula (I) may be the same or different and have 12 to 24 carbon atoms, preferably
16-20 linear or branched alkyl or alkenyl groups. When the number of carbon atoms is less than 12, the fabric after washing cannot have sufficient flexibility and texture, and when the number of carbon atoms exceeds 24, it does not dissolve transparently at low temperatures.
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 number of moles of polyoxyethylene group or polyoxypropylene group added is preferably 1 to 5, particularly preferably 1 to 5.
3. X is a halogen atom, CH ₃ SO ₄ or C ₂ H ₅
SO ₄ , preferably a halogen atom. Halogen atoms include chlorine, bromine or iodine,
Preferably, it is chlorine.

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 derived from soybean oil fatty acid. And dialkyldimethyl ammonium salts of the group. In particular, dioleyl dimethyl ammonium salt is preferred. The cationic surfactant may be used alone or in combination of two or more. The iodine value of the cationic surfactant used as a whole is 40 to 100, preferably 60 to 90. The system containing this cationic surfactant is transparent, but if the iodine value is less than 40, the cause is not clear, but a cloudy precipitate is deposited at a low temperature, which is not preferable. The content of the cationic surfactant is 1 to 5% by weight in the composition. If the amount is less than 1% by weight, flexibility is not given to the washed fiber, and
If the content is more than 10% by weight, a cloudy precipitate tends to precipitate at a low temperature, and the detergency decreases.

In the formula (II), R ⁵ has 10 to 20 carbon atoms.
Or an alkyl or alkenyl group having 6 to 1 carbon atoms
An alkylphenyl group having two 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
To 12 polyoxyethylene alkyl or alkenyl ethers or 6 to 12 carbon atoms, preferably 8 to
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 to 30% by weight.
5 to 25% by weight. If it is less than 10% by weight, the detergency is weak, and the stability at low temperatures is reduced. On the other hand, if it exceeds 30% by weight, the solubility at room temperature is poor, and it tends to be gel-like.

In the formula (III), R ⁶ has 10 to 2 carbon atoms.
2, preferably 12 to 18 linear or branched alkyls, 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. Formula (III)
Is added in order 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.
It is. If the content is less than 0.5% by weight, the solubility of the composition is poor,
A film may be formed on the liquid surface with the passage of time. If the amount exceeds 8% by weight, not only the foaming becomes poor, 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 3 carbon atoms, and is preferably an ethylene group. R ¹⁰ is a linear or branched alkyl group having 1 to 4 carbon atoms, preferably a butyl group. n is 2-3. Specific examples of the glycol ether represented by the formula (IV) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, and dipropylene glycol. Monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether and the like, preferably, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, particularly preferably, diethylene glycol monobutyl ether, triethylene glycol Glycol monob It is an ether. The glycol ether is added for improving the solubility upon dilution with water, and its content is 1 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 50% by weight in the composition. 50% by weight. If the amount is less than 1% by weight, improvement in solubility in water and stability at low temperatures are not recognized. On the other hand, if it exceeds 70% by weight, stability at normal temperature and low temperature is not recognized.

In the present invention, two or more components of the formulas (II) to (IV) can be used in combination. In the present invention, the weight ratio of the total amount of the nonionic surfactant represented by the formula (II) and the amine oxide represented by the formula (III) to the cationic surfactant represented by the formula (I) is 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 smaller than 1:20, the effect of imparting flexibility to the fiber is not exhibited, and if it is larger than 1: 4, the low-temperature stability is reduced. And the detergency decreases.

The composition of the present invention can be produced by mixing and dissolving desired components by a conventional method. Further, in order to improve detergency or prevent recontamination, polyvinyl alcohol, carboxymethyl cellulose, A water-soluble polymer such as hydroxypropylmethylcellulose and hydroxybutylcellulose can be blended. Further, for example, an enzyme such as a protein hydrolase, a lipid hydrolase, a starch hydrolase, a lytic enzyme and the like can be added. Further, the composition of the present invention may optionally contain additives commonly used in this type of detergent, such as fragrances, bactericides, pigments, and dyes.

In using the composition of the present invention,
The composition was prepared by adding 200 to 2000 times the volume of water or hot water (1
0-30 ° C.), and the laundry is immersed in this for a short period of time, for example, 10-30 minutes, and then rinsed to remove dirt without any problem such as shrinkage of clothes. Can be washed well. The composition of the present invention is particularly suitable for washing products requiring delicate washing, such as silk and wool. Further, the composition of the present invention in the form of a stock solution,
If used in the same manner as a normal stain remover, it can be suitably used as a stain remover for oily stains.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In Examples,% in the concentration and the amount used is% by weight. Further, a stability test, a solubility (dispersibility in water) test and a detergency test were performed as follows. The water used in these tests was tap water, and the detergency test was conducted on the basis of immersion 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 taken in a 100 ml screw tube, left in a thermostat at -5 ° C and 25 ° C for 1 month, and its appearance was visually judged. In addition, a viscometer (Co., Ltd.)
The viscosity was measured by a BM type viscometer manufactured by Tokimec Corporation, and this judgment was also evaluated. The evaluation criteria are as follows. ◎ Transparent, fluid, viscosity less than 2000 cps ○ Translucent, fluid, viscosity less than 2000 cps × Gelation, cloudiness, separation, viscosity 2000 cps or more

Flexibility test 500 ml of a 0.1% aqueous solution of the liquid detergent composition at 30 ° C.
Inside, a 20 cm × 20 cm silk cloth was immersed for 10 minutes, and then shaken and rinsed twice with fresh water, then dehydrated with a towel dry and air-dried. This washing operation was defined as one cycle, and repeated five times. After 5 cycles, a low-temperature iron was applied to form a test cloth. A pair of the cloth was compared with an uncleaned cloth by touch by eight judges, and the cloth was judged as follows. The evaluation criteria are as follows. ○ Softer than unwashed silk × Harder than unwashed silk

Dispersibility test-1: Solubility test upon dilution with water A beaker containing 1 liter of tap water (20 ° C.) was stirred at a constant speed, and 1 g of the detergent composition weighed with a syringe was added to complete the addition. The time until dissolution 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 Five pieces of 5 cm × 5 cm artificially stained cloth (wet artificially stained cloth manufactured by Washing Science Association) were immersed in 1 liter of the detergent composition aqueous solution.
It was pickled and washed in a beaker. The washing conditions are as follows. <Washing conditions> Washing time: 20 minutes Washing temperature: 20 ° C Washing agent concentration: 0.1% Rinsing: Shaking rinse Dehydration: Towel drying Drying: Iron <Soil component of artificially stained 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% Each reflectance before and after washing was measured with a color computer (Nippon Denshoku Industries Co., Ltd., color difference meter model ND-1001DP), and calculated by the following equation.

[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 cleaning

Dispersibility test-2: Dispersibility test upon dilution 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 weighed with a syringe was added to the position, and the position was stirred with a stirrer for 20 seconds, left for 10 minutes, and the detergent solution was collected from the position and the concentration of the detergent solution. Was measured by a method for quantifying a cationic surfactant (JIS K3362-5.4.3). Furthermore, the numerical value of the actually measured density when the theoretical density (0.1%) is set to 100 is shown.

Detergency Test-2 A detergency test was conducted at the detergent concentration determined in 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 made from the results of the performance evaluation of each cleaning composition. The evaluation criteria are as follows for Table 1 and Table 2, respectively. Evaluation criteria in Table 1 ：: A composition in which the results of the stability test (normal temperature and low temperature), the flexibility test and the dispersibility test-1 are all ◎, and the result of the detergency test-1 is 17 or more. : One of the results of the stability test (normal temperature and low temperature), the flexibility test and the dispersibility test-1 is ○, the others are ◎,
And a composition in which the result of the detergency test-1 is 17 or more. ×: a composition in which at least one of the results of the stability test (normal temperature and low temperature), the flexibility test and the dispersibility test-1 is × Evaluation criteria ◎: stability test (normal temperature and low temperature) and dispersibility test-
Composition where all the results of 1 are ◎: Stability test (normal temperature and low temperature) and dispersibility test-
Compositions in which one or two of the results of 1 are ○ and all others are ◎: Compositions in which at least one of the results of the stability test (normal temperature and low temperature) and the dispersibility test-1 are ×

Examples 1 to 9 and Comparative Examples 1 to 10 Liquid detergent compositions having the compositions shown in Tables 1, 2 and 3 were produced according to a conventional method, and were subjected to various tests and evaluations. First, the composition and the amount of the glycol ether represented by the formula (IV) were fixed, and each composition was prepared by changing the kind and the amount of the compound represented by the formula (I) to the formula (III). The stability test, flexibility test, detergency test-1 and dispersibility test-1 of each composition were evaluated and comprehensively evaluated. 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 surfactant represented by the formula (I) in Comparative Examples 2 and 3 is obtained. The amount of the activator in the composition is 1
When the amount is outside the range of 5 to 5% by weight, the amount of the nonionic surfactant represented by the formula (II) in Comparative Examples 4 and 5 is 10 to 10% by weight.
30% by weight and the formula in Comparative Example 6
If the compounding amount of the amine oxide represented by (III) is out of the range of 0.5 to 8% by weight, stability and flexibility will be reduced.

Next, in order to demonstrate that poor solubility of the detergent composition in water may cause a reduction in detergency and uneven cleaning, compounds represented by the formulas (I) to (III) may be used. The dispersibility test-1, 2 and the detergency test-2 of each composition when the type and the amount of the glycol ether represented by the formula (IV) were changed while the type and the amount of the glycol ether were fixed were evaluated. Was. Table 2 shows the results.

[0035]

[Table 2]

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

Next, the types and amounts of the compounds represented by the formulas (I), (II) and (III) are fixed, and the types and the amounts of the glycol ethers represented by the formula (IV) are changed. The stability test and the dispersibility test-1 of each detergent composition in the case of the evaluation were evaluated and comprehensively evaluated. Table 3 summarizes the results.

[0038]

[Table 3]

As shown in Examples 7, 4, 1, 8, 5, 6 and 9 and Comparative Examples 7 to 10, when the glycol ether represented by the formula (IV) was not blended, Was poor in solubility (dispersibility), causing a reduction in detergency and uneven cleaning, and in terms of stability, the properties were gelled, clouded or separated.

From these results, the liquid detergent composition of the present invention is excellent in storage stability, detergency, and solubility (dispersibility) upon dilution with water, as compared with the composition of the comparative example. It is clear that.

Example 9 The following ingredients were heated and stirred at 60 ° C. to make them uniform. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Ingredients (% by weight) Dioleyldimethylammonium chloride 4.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 23.0 Lauryl dimethylamine oxide 2.0 Diethylene glycol monobutyl ether 10.0 Citric acid Sodium 0.2 Citric acid 0.05 Preservatives 0.05 Fragrance 0.5 Purified water 60.2

Example 10 The following ingredients were heated and stirred at 60 ° C. to make them uniform. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Incorporation amount (% by weight) Dioleyldimethylammonium chloride 1.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 15.0 Lauryl dimethylamine oxide 1.0 Diethylene glycol monobutyl ether 50.0 Preservative 0.05 Purified water 32.95

Example 11 The following ingredients were heated and stirred at 60 ° C. to make them uniform. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Incorporation amount (% by weight) Dioleyldimethylammonium chloride 4.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 18.0 Lauryl dimethylamine oxide 7.0 Diethylene glycol monobutyl ether 5.0 Triethylene Glycol monobutyl ether 5.0 Sodium citrate 0.2 Citric acid 0.05 Preservatives 0.05 Fragrance 0.5 Purified water 60.2

Example 12 The following ingredients were heated and stirred at 60 ° C. to make them uniform. This was cooled with stirring to produce a liquid cleaning composition. Ingredients Incorporation amount (% by weight) Dioleyldimethylammonium chloride 5.0 Polyoxyethylene (n = 9) C ₁₂ -C ₁₅ mixed alkyl ether 20.0 Lauryl dimethylamine oxide 4.0 Diethylene glycol monobutyl ether 20.0 Preservative 0.05 Fragrance 0.5 Dye 0.1 Purified water 50.35

[0045]

According to the present invention, it has a practical detergency in washing silk products, wool products, fashionable clothes, etc., is stable at normal and low temperatures, and has excellent solubility when diluted with water. A liquid detergent composition for immersion washing is obtained.

[Brief description of the drawings]

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

[Description of Signs]: 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.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-4-4298 (JP, A) JP-A-4-76099 (JP, A) JP-A-4-57962 (JP, A) JP-A-50- 77289 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/62 C11D 1/72 C11D 1/75 C11D 3/20 C11D 3/43

Claims (3)

(57) [Claims] 1. A compound of formula (I): Wherein R ¹ and R ² are an alkyl or alkenyl group having 12 to 24 carbon atoms, R ³ and R ⁴ are a methyl group, an ethyl group, a polyoxyethylene group or a polyoxypropylene group, X is a halogen atom, CH ₃ SO ₄ or C ₂ H ₅ SO ₄
And 1 to 5% by weight of a cationic surfactant having an iodine value of 40 to 100 and a mixture of two or more selected from compounds represented by the following formula (II): (Wherein, R ⁵ represents 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 represents 5 to 15). ３０30% 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): (Wherein, R ⁹ represents an alkylene group having 2 to 3 carbon atoms, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, and n represents 2 to 3). ~ 5
0% by weight of a liquid detergent composition. 2. The weight ratio of the total amount of the components of the formulas (II) and (III) to the component of the formula (I) is from 1:20 to 1:
The liquid detergent composition according to claim 1, which is 4. 3. The method according to claim 1, which is for pickling and washing.
A liquid detergent composition according to the above.