JP3484748B2 - Liquid detergent composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent liquid detergent for use only for placing, and more particularly, for cleaning even small stains such as silk products, wool products, and fashionable clothes. Has an appropriate detergency and shape retention function for clothing that needs to be
The present invention relates to a liquid detergent which has good foam removal, does not impair an excellent texture, and has excellent storage stability. 2. Description of the Related Art Conventional soaking washing is generally called washing machine,
It refers to pre-washing before washing with hand washing (fir washing) or to soaking in a detergent solution containing an enzyme to enhance washing power. In this cleaning method, it is necessary to wear clothing for a long time (for example, overnight) to sufficiently remove dirt. [0003] Conventionally, in the washing of clothes in the home, after washing with a detergent containing an anionic surfactant or a nonionic surfactant as a main component, a feeling of fiber and an antistatic property are imparted. The softening treatment is carried out with a softener containing a cationic surfactant as a main component. However, this method requires two operations, i.e., washing and imparting flexibility, which is complicated. Therefore, Japanese Patent Publication No. 47-4750 and Japanese Patent Application Laid-Open No. 57-126896 discuss a one-pack type cleaning composition which simultaneously performs the above operations. This one-pack type detergent composition is mainly composed of a nonionic surfactant or a semipolar surfactant, and has a monoalkyl or dialkyl cationic surfactant having a long-chain saturated alkyl group in the molecule. Is blended as a softener component. Further, JP-A-4-4298 discloses an unsaturated dialkyl-type cationic surfactant, a polyoxyethylene alkyl ether-type nonionic surfactant, and an amine oxide-type nonionic surfactant for the purpose of improving the feeling of washing. Proposal of a cleaning composition combining agents. [0004] Delicate garments such as silk and wool need to be washed even in a slightly soiled state, but if they are washed by conventional soaking, it takes a long time. Requires a problem that the clothes shrink. Further, the conventional detergent composition for immersion washing has a drawback that foaming is poor at the time of rinsing since the composition 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 has a drawback that when stored for a long period of time, turbidity or precipitation occurs at a low temperature and the appearance of the composition is impaired. [0005] The present invention has an appropriate detergency to remove dirt from a delicate garment by immersion for a short period of time and a shape retaining function without shrinkage, has good foam removal, does not impair excellent texture, and It is intended to provide a liquid detergent composition having excellent storage stability. [0006] In order to solve the above-mentioned problems, studies have been repeated to find that a specific non-ionic surfactant and a cationic surfactant having an iodine value in a specific range can be used. By combining the water-soluble silicone derivatives in a specific weight ratio, a liquid detergent composition having a unique characteristic has 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 1
2/1, which is a liquid detergent composition. a. A nonionic surfactant represented by the formula (1): [0007] (Wherein R ¹ represents an alkyl or alkenyl group having 10 to 22 carbon atoms, n represents 5 to 15, and m represents 1 to 5). B. 100 cationic surfactants. [0009] (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. Nonionic surfactants represented by the formula (1) is R ¹ is an alkyl or alkenyl group having 10 to 22 carbon atoms, such as lauryl group, myristyl group, palmityl group, a stearyl group, an oleyl group, a coconut oil alkyl Group, tallow alkyl group, etc., and if the carbon number is 9 or less, the texture is impaired,
Above 23, storage stability deteriorates. n is 5 to 15,
Indicates the average number of moles of ethylene oxide added. When n is less than 5, storage stability is deteriorated. When n is more than 15, foam disappears during rinsing. m is from 1 to 5 and represents the average number of moles of propylene oxide added. If m is less than 1, foam disappears during rinsing, the texture is impaired, and if it exceeds 5, storage stability deteriorates. Ethylene oxide and propylene oxide are block additions, respectively, and the random addition impairs the feeling. 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 an alkyl group or an alkenyl group having 12 to 24 carbon atoms, for example, a lauryl group, a myristyl group, a palmityl group, a stearyl group, Examples include a behenyl group, an oleyl group, a coconut oil alkyl group, and a tallow alkyl group. When the number of carbon atoms is 11 or less, the texture is impaired, and when the number of carbon atoms is 25 or more, the storage stability deteriorates. 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 impaired. X is a halogen atom, CH ₃ SO ₄ ,
Or 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. If the iodine value is less than 40, the shape-retaining function and texture are impaired. If the iodine value exceeds 100, the foam disappears during rinsing. Examples of the water-soluble silicone derivative of the component c include polyether-modified silicone derivatives, alcohol-modified silicone derivatives, amino-modified silicone derivatives, epoxy-modified silicone derivatives, and carboxyl-modified silicone derivatives. a is 10 to 50% by weight,
If the amount is less than 50% by weight, the detergency and storage stability decrease, and
If it exceeds, the foam runs out poorly. [0013] b is from 1 to 15% by weight, but if it is less than 1% by weight, the shape-retaining function and texture are impaired, and if it exceeds 15% by weight, the detergency and storage stability are reduced. Although c is 0.1 to 5% by weight, if it is less than 0.1% by weight, the shape-retaining function and texture are impaired, and the foaming becomes poor. If it exceeds 5% by weight, the detergency and the storage stability decrease. The weight ratio between a and b + c is 10 /
When the value of "a" is larger than this, the shape retention function and the texture are impaired, and the foaming becomes poor. When the value of "a" is smaller, the detergency and storage stability are reduced. [0014] The detergent composition of the present invention may contain components generally blended as required, for example, solubilizers 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, and bactericides such as paraoxybenzoate, phenoxyethanol, benzalkonium chloride, and didecyldimethylammonium chloride Chelating agents such as ethylenediaminetetraacetic acid derivative, citric acid, and trisodium nitrilotriacetate; ultraviolet absorbers such as benzophenone derivatives and benzotriazole derivatives; and other dyes and fragrances can be contained to the extent that the effects of the present invention are not impaired. . The present invention will be described more specifically with reference to examples. The test methods and evaluation methods performed in the examples are shown below. The water used for these tests is tap water. The feelability test, shape retention test, detergency test, and foam removal test are all examined on the basis of immersion washing. The silk cloth used is 100% silk satin woven cloth from Tango. (1) Storage stability The liquid detergent composition was prepared at about 70 ° C., and then cooled to about 40 ° C. Take this in a 100 ml screw tube, and
It was left in a thermostat at 5 ° C. for one month, and its change in appearance was visually determined, and evaluated in the following three stages. 〇: Good storage stability (in a transparent dissolved state, with fluidity) △: Slightly poor stability (slightly turbid, with fluidity) ×: Poor stability (separation, sedimentation is recognized or solidified) [ (2) 500 ml of a 0.1% by weight aqueous solution of the hand-cleaning liquid detergent composition was placed in a 1-liter beaker, and a 20 cm × 20 cm silk cloth was immersed in the beaker for 10 minutes, followed by rinsing twice. , Dried for 10 seconds and dried. This washing operation was defined as one cycle and repeated five cycles. After 5 cycles, a low temperature iron was applied to form a test cloth. Twenty women were panelists, and a pair of this cloth was compared with an unwashed cloth based on the feeling of touch. 3 points when the test cloth felt very softer than unwashed, 2 points when the test cloth felt slightly softer,
The average value of the 20 subjects was determined as 1 point when the person felt slightly hard and 0 point when the person felt very hard, and evaluated in the following three grades. Good texture (average value of 2.5 points or more) Slightly textured (average value of less than 2.5 points and 1.5 points or more) Poor texture (average value of less than 1.5 points) (3) Shape retention 30cm x 30cm Silk raw cloth at 20 ℃, 65%
The humidity was adjusted with 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; lateral b ₁ ^0, b ₂ ^0,
b ₃ ^0), it was the length of the original length. The three test cloths obtained in the above were placed in one 1-liter beaker, and were soaked and washed. The concentration of the liquid detergent composition was 0.1% by weight, and the water temperature was 20 ° C. As for rinsing, shaking was performed twice in a 1-liter beaker. Next, the test cloth is put on the wall of the dehydration tub of the washing machine, and after the rotation is stabilized, dehydration is performed for 10 seconds. Then, the cloth is laid flat on a net, dried and dried at 20 ° C. and 65% RH for 4 hours or more. Conditioned. Further, the length between the marks previously marked was measured again (vertical a ₁ ^W , a ₂ ^W , a ₃ ^W ; horizontal b
₁ ^W , b ₂ ^W , b ₃ ^W ), and the shrinkage of the test cloth was calculated from the following equation. ## EQU1 ## 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 washing (vertical _{^{a 1 W, a 2 W,}} a 3 W; horizontal _{^{b 1 W, b 2 W,}} b 3 W) vertical, and the average shrinkage rate calculated lateral from each of the three places, the From the average value, the shape retention was evaluated in the following three grades. High form retention (vertical and horizontal shrinkage less than 5.0%) Medium form retention (vertical and horizontal shrinkage of 5.0% or more1
(Less than 0.0%) Low shape retention (vertical and horizontal shrinkage is 10.0% or more) (4) Detergency A 500 ml aqueous solution of the liquid detergent composition is placed in a 1 liter beaker, and a 10 cm × 10 cm artificial Two contaminated cloths and two white cloths were immersed, adjusted so that the bath ratio was 1: 100, and immersed and washed. The cleaning conditions and the composition of the artificially stained 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 rotation of the dehydration tank stabilizes <Soil composition of artificially stained cloth> Oleic acid 15.0 Palmitic acid 7.5 Myristic acid 7.5 tallow hardened oil 30.0 cholesterol 10.0 squalene 5.0 cetyl alcohol 10.0 paraffin 15.0 This was made by dispersing carbon black into artificial soil, and this was used to contaminate a white cloth to make an artificially contaminated cloth. After drying the contaminated cloth, color computer (manufactured by Suga Test Machine Co., Ltd.)
Measure the surface reflectance with, calculate the detergency from the following formula,
Evaluation was made in the following three stages. ## EQU2 ## Excessive detergency (25% or more detergency) Good detergency (15% or more and less than 25% detergency) Low detergency (less than 15% detergency) (5) Defoaming liquid cleaning 500 ml of a 0.1% by weight aqueous solution of the agent composition was placed in a 1-liter beaker, and a 20 cm × 20 cm silk cloth was immersed in the beaker for 10 minutes, followed by rinsing twice. Twenty women were panelists, and the cloth was tested for the feel to touch. If you touch it, you will get slim
The average score of the 20 subjects was calculated based on the following three points, with 1 point when the user felt that they felt slightly slimy, and 2 points when they felt almost non-slimy. Good foam removal (average value of 1.5 points or more) Slightly poor foam removal (average value of 1.0 to less than 1.5 points) Poor foam removal (average value of less than 1.0 point) Examples 1 to 10 and Comparative Examples 1 to 10 Samples having the composition shown in Tables 1 to 4 were prepared, and the performance was evaluated. The results are shown in Tables 1 to 4. The unit in the table indicates% by weight. [Table 1] [Table 2] [Table 3] [Table 4] In Tables 1 to 4, (Note 1) In 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 component is a compound of the 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; The iodine value is 70) ''
It was used. (Note 4) Nissan Cation 2-OLR manufactured by NOF Corporation
(The main components are those in which R ² and R ³ in the formula (2) are oleyl groups, R ⁴ and R ⁵
Is a compound having 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, it can be seen that the compositions of Examples 1 to 10 of the present invention have an appropriate detergency for removing dirt by short-time immersion washing, a form-retaining function without shrinkage, and a foam removal property. well,
It is clear that the composition does not impair the excellent texture and has excellent storage stability. In the composition of Comparative Example 1, 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 a was over 50% by weight, foam removal was poor. Since the composition of Comparative Example 3 has b less than 1% by weight, the texture is poor and the shape retention is low. Comparative Example 4
The composition (b) has a poor storage stability and low detergency because b exceeds 15% by weight. The composition of Comparative Example 5 has a poor feel and a low form retention because c is less than 0.1% by weight.
Poor foam. Since the composition of Comparative Example 6 had c exceeding 5% by weight, storage stability was poor, and detergency was weak. Comparative Example 7
The composition (a) has a poor hand feeling, a low form retention, and poor foam removal because the weight ratio of a to b + c is greater than 10/1. The composition of Comparative Example 8 has a poor storage stability and a low detergency because the weight ratio of a to b + c is smaller than 2/1. Since the composition of Comparative Example 9 uses a nonionic surfactant of the formula (1) where m is 0, the composition has low shape retention and poor foam removal. Comparative Example 10
The composition of Example 1 uses lauryl dimethylamine oxide in place of a, and therefore has poor storage stability, poor foam removal, low form retention, and low detergency. The liquid detergent composition of the present invention has an appropriate detergency for removing stains by short-time immersion washing, and a function of maintaining a shape without shrinkage, and has excellent foam removal and excellent properties. Since it is a liquid detergent composition that does not impair the texture and has excellent storage stability, it is most suitable for washing delicate clothes that need to be washed even with slight stains such as silk products, wool products, and fashionable clothes.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-153300 (JP, A) JP-A-4-220500 (JP, A) JP-A-1-1322692 (JP, A) JP-A-4- 4298 (JP, A) JP-A-5-239493 (JP, A) JP-A-54-157110 (JP, A) JP-A-3-207798 (JP, A) JP-A-3-134097 (JP, A) JP-A-62-161899 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1/00-17/08

Claims (1)

(57) [Claim 1] It contains the following a, b, and c, wherein 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). Embedded image (Wherein R ¹ represents an alkyl or 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) and having an iodine value of 40 to 100. Embedded image (Wherein R ² and R ³ are an alkyl or alkenyl group having 12 to 24 carbon atoms, R ⁴ and R ⁵ are a methyl group, an ethyl group or — (CH ₂ CH ₂ O) _P H 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 derivatives.