JP2863137B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can effectively wash various textile products made of wool, acrylic, polyester, or a blend of these fibers, for example, so-called fashionable clothing, and furthermore, has a good texture and dimensional stability. The present invention relates to a liquid detergent composition having excellent properties.

[0002]

2. Description of the Related Art Clothes differ not only in the washing method but also in the components, composition and solvent of the detergent used, depending on the type of the material. Generally, a mark indicating the washing conditions is sewn on clothing, and designation of dry washing using a solvent (dry mark), washing conditions in a water system, and the like are displayed. For example, clothing made of animal hair, particularly wool clothing, is generally often designated dry because of its properties. Dry washing requires special solvents and equipment, so washing at home is difficult, and the only way to do this is to ask a specialized cleaning shop. However, some of the dry mark garments can be washed with water-based detergents using a neutral detergent, and the development of a detergent with an excellent finish that does not damage fibers has made it possible to wash at home without hesitation. In addition, the development of textile processing technology has improved the durability during washing, and has led to the launch of a washing machine with a washing mode for dry mark clothing. It's even easier.

[0003] As a condition for washing these dry mark garments in a water system, it is preferable to wash them by hand or by applying a weak mechanical force in order to maintain the texture without damaging the fibers. However, clothing such as wool is not sufficiently wetted by water-based washing liquid and has poor permeability to the interior of textiles and the like, so that the washing property is insufficient, and improvement of this point is strongly demanded. .

As light detergents such as those for dry mark clothing, polyoxyethylene alkyl ethers, polyoxyethylene alkyl sulfates, alkylbenzene sulfonates and the like are widely used as main cleaning bases. ing. In addition, there is little skin irritation,
Attention has been paid to a technique in which an alkyl glucoside or an amine oxide is blended because it has an excellent hand feel during use (Japanese Patent Publication No. 5-75799, Japanese Unexamined Patent Publication No. 4-11698).
JP-A-3-188195, JP-A-57-96096, JP-A
57-105496, JP-A-57-205499, JP-A-62-215699
JP-A-1-247496, JP-A-6-271457, JP-A-5-247492). In particular, by mixing ether-type nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl sulfate, alkyl glucoside and amine oxide, those suitable for the performance of the intended use have been found. I have.

However, these are mainly used for kitchen detergents and shampoos, and detergents for liquids having an alkaline or acidic pH, and as a neutral light detergent, the wettability of dry mark clothing, especially wool clothing. Research to improve the cleanliness sufficiently and to enhance the detergency has not yet been sufficiently conducted.

In order to prevent shrinkage of wool products and the like, a technique using a combination of an amino-modified silicone, a specific dialkyl-type cationic surfactant and a water-soluble silicone, a polyamide softener and a functional polyalkylene oxide polyol has been proposed. It has been disclosed (JP-A-3-207796).
JP-A-3-207798, JP-A-6-313193, JP-A-7-242897, JP-A-63-199294, JP-A-7-145400
issue). However, wool products and the like are mainly washed using a hand washing course of a fully automatic washing machine, and press-washing in lukewarm water, so the shrinkage prevention effect of wool products is insufficient even by these techniques. Therefore, there is a strong need for a laundry detergent having a further improved shrinkage preventing effect.

Further, wool, acrylic, polyester,
Alternatively, in so-called fashionable clothes made of these blended fibers, etc., the flexibility of washing is also emphasized, but as described above, the wet mark and anti-shrinkage required for dry mark clothing are provided, and further flexibility is provided. No composition has been found that can provide the same.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific amino-modified silicone derivative and a specific HLB (hydrophilic / lipophilic balance) ether type Nonionic surfactant and HLB
When blended with two types of higher alcohol ethoxylate type nonionic surfactants with small values and a small width of ethylene oxide addition mole number distribution, appropriate detergency for clothing made of wool, acrylic, polyester etc. Was obtained, and a liquid detergent composition having further excellent texture and dimensional stability was found, and the present invention was completed.

That is, the present invention provides (a) a compound represented by the following general formula (I):
0.05-5% by weight of an amino-modified silicone derivative represented by
And (b) a surfactant containing 95 to 75% by weight of the following nonionic surfactant (i), 5 to 70% by weight of a surfactant containing 5 to 15% by weight of the following nonionic surfactant (ii), and (a): (b)
Wherein the weight ratio of (a) :( b) = 1: 100 to 1: 5 is provided.

[0010]

Embedded image

Wherein l is 100 to 600, and m and n are l: m = 100: 1 to 1
0: 1, and m: n = 1: 10 to 10: 1. R: an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group R ¹ ; an alkyl group having 1 to 4 carbon atoms, which may be different from each other. A: A group represented by the following (A) or a group represented by the (A) and (B), and in the latter case, the ratio of (B) in A is 50
Mol% or less.

[0012]

Embedded image

A; 2 to 6 R ² ; a hydrogen atom or an alkyl group having 1 to 4 carbon atoms p; 1 to 6 q; 1 to 20 r; 0 to 20 R ³ ; an alkyl group B having 1 to 18 carbon atoms; _{- (CH 2) a -O- (} C 2 H 4 O) x - (C 3 H 6 O) y -R 4 or R ¹ R ^4; alkyl group having 1 to 10 carbon atoms x; 1 to 20 y; 0 to 20 is indicated. <Nonionic surfactant (i)> Nonionic surfactant represented by the following general formula (i): R ₁ O (R ₂ O) _n R ₃ (i) (wherein R ₁ is a linear or A branched chain alkyl group or alkenyl group having 8 to 18 carbon atoms, or an alkylphenyl group having 12 to 22 carbon atoms, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents hydrogen or a methyl group; Or an ethyl group.
n is the number of moles of alkylene oxide added so that the HLB value of (i) is 12 to 15. <Nonionic surfactant (ii)> A compound represented by the following general formula (ii), having an HLB value of 7 to 10, and having a content of a compound of n = 0 of 4% by weight or less and having the highest content. added moles n _max of containing 5 to 15 parts by weight of a nonionic surfactant which satisfies the following formula (a) with respect to said surfactant system 100 parts by weight. R ₄ O (CH ₂ CH ₂ O) _n R ₅ (ii) (wherein R ₄ is a linear or branched alkyl group or alkenyl group having an average of 8 to 18 carbon atoms or an alkyl group having a total of 12 to 22 carbon atoms) Represents a phenyl group, R ₅ is hydrogen or a methyl group, and n is the number of moles of ethylene oxide added so that the HLB value of (ii) is 7 to 10.)

[0014]

(Equation 2)

<Component (a)> The amino-modified silicone derivative used as the component (a) in the present invention is disclosed in the above-mentioned publications (JP-A-60-215099;
207796 and JP-A-3-207798) are different from those of the silicone compound in the structure and action and effect.

In the present invention, the component (a) is incorporated in the composition in an amount of 0.05 to 5% by weight, preferably 0.1 to 3% by weight. If the amount of the component (a) is less than 0.05% by weight, a sufficient felt shrinkage preventing effect for wool products and a sufficient texture improving effect for acrylic products and polyester products cannot be obtained. Further, the content exceeding 5% by weight does not change effectively and only increases the price, which is not preferable, and impairs the storage stability of the liquid detergent.

<Component (b)> In the present invention, a surfactant containing the following two nonionic surfactants (i) and (ii) as component (b) (hereinafter referred to as surfactant) Agent system) is used.

(B) In the surfactant system of the composition of the present invention
As the component, the following general formula (i) R ₁ O (R ₂ O) _n R ₃ (i) (wherein, R ₁ is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, or represents the total alkylphenyl group having a carbon number of 12 to 22, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ is hydrogen, methyl or ethyl.
n is the number of moles of alkylene oxide added so that the HLB value of (i) is 12 to 15. ) Is used.

HLB of the nonionic surfactant (i)
The value is between 12 and 15, but if the HLB value is greater than 15,
The permeation rate of the washing water into the cloth is reduced, so that the wetting is deteriorated and the washing power is also reduced. When the HLB value is smaller than 12, the detergency decreases. Also, HLB
Nonionic surfactants having a range of 12 to 15 have the best texture. In the present invention, the HLB value was calculated by a calculation method proposed by Griffin (Noboru Moriyama, “Chemistry of Dispersion and Aggregation”, page 13, Sangyo Tosho Publishing, 1995). In such nonionic surfactants, it is preferable that the distribution of the alkylene oxide be obtained by using a conventional alkali catalyst or be broadened by mixing two kinds.

In the present invention, an ether type nonionic surfactant having a low HLB value and a narrow-range oxyethylene chain represented by the following formula (ii) is further used:
By blending 5 to 15% by weight in the surfactant system, while maintaining the detergency, the penetration rate into clothing made of animal hair such as wool is remarkably improved, and further the texture is improved. I found that. R ₄ O (CH ₂ CH ₂ O) _n R ₅ (ii) (wherein R ₄ is a linear or branched alkyl group or alkenyl group having an average of 8 to 18 carbon atoms or an alkyl group having a total of 12 to 22 carbon atoms) A phenyl group, R ₅ is hydrogen or a methyl group, and n is the number of moles of ethylene oxide added so that the HLB value of (ii) is 7 to 10.) It is represented by the general formula (ii) Non-ionic surfactants are HLB
The value is 7 to 10, preferably 7.5 to 9.5, and n = 0
The content of the compound (unreacted alcohol) is 4% by weight or less,
Preferably, it must be 2% or less. The addition mole number n _{max of the} compound having the largest content is represented by the following formula (A):
Is satisfied.

[0021]

(Equation 3)

Preferably, the number of added moles n _max is at least 70% in the above formula (A).

The incorporation of such a nonionic surfactant having a very sharp distribution of oxyethylene chains increases the rate and amount of adsorption of the present detergent composition to clothing,
It is thought that the penetration rate and the wettability of the cleaning liquid into clothing such as wool are improved, and further the texture is improved.

In the present invention, the surfactant system of the component (b)
It is necessary to contain 95 to 75% by weight of the nonionic surfactant (i) and 5 to 15% by weight of the nonionic surfactant (ii), and the nonionic surfactant (i) is less than 75% by weight. Then
Detergency decreased, 15% by weight of nonionic surfactant (ii)
If it exceeds, the texture of the acrylic product will be impaired.
On the other hand, when the nonionic surfactant (i) exceeds 95% by weight, the permeation rate of the cleaning liquid particularly to the wool product becomes slow, and as a result, the detergency decreases, and further the nonionic surfactant (ii) becomes 5%. Since the content is less than the weight%, the texture of the wool product is reduced.

Among the surfactants contained in the component (b), components other than the nonionic surfactants (i) and (ii) include:
The following are mentioned.

As components other than the nonionic surfactants (i) and (ii) in the surfactant system of the composition of the present invention, anionic surfactants are used. Specifically, alkyl benzene sulfonate, alkane sulfonate (SAS),
Anionic surfactants having a hydrophilic group with -SO ₃ ^- groups such as olefin sulfonates, sulfates of primary and secondary higher alcohols, sulfates of polyoxyethylene alkyl ethers, and soaps, polyoxyethylene alkyls -OSO ₃ such as salts of carboxymethylation product of ether ^-
A surfactant having a hydrophilic group such as a group or —COO 2 ^— group is a typical example. In particular, a sulfate ester obtained by adding an average of 1 to 6 moles of ethylene oxide to an alcohol having 8 to 18 carbon atoms is preferable. As the counter ion of the above-mentioned anionic surfactant, Na ion, K ion and ammonium ion are suitable, but Mg ion is also included therein.

The component (b) other than the nonionic surfactants (i) and (ii) in the surfactant includes the following general formula (iii) R ₆ (OR ₇ ) _x G _y (iii) ( In the formula, R ₆ represents a linear or branched alkyl group having 8 to 18 carbon atoms, an alkenyl group, or an alkylphenyl group; R ₇ represents an alkylene group having 2 to 4 carbon atoms; 6 is a residue derived from the reducing sugar, and x has an average value of 0 to 5
And y represents a number whose average value is 1.0 to 2.0. And / or the following general formula (iv)

[0028]

Embedded image

(Wherein R ₈ is a straight-chain or branched-chain carbon number of 8 to
18 represents an alkyl group or an alkenyl group, and R ₉ and R ₁₀ represent a methyl group or an ethyl group. The amine oxide represented by) is used.

In the present invention, the amount of the component (b) in the surfactant composition is 5 to 70%, preferably 10 to 40%.

In the present invention, the ratio (weight ratio) of the component (a) to the component (b) is (a) :( b) = 1: 100 to 1: 1.
5, preferably 1:50 to 1:10. When the ratio of the component (b) to the component (a) exceeds 100, the effect of the texture and dimensional stability of the component (a) becomes insufficient. If the ratio of the component (b) to the component (a) is less than 5, the storage stability of the liquid detergent composition will decrease.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid detergent composition of the present invention contains the above components (a) and (b) and is suitable as a liquid detergent containing water as a main medium. Moisture is 30-90% by weight,
Preferably it is 45 to 80% by weight. Within this range, the liquid detergent composition of the present invention is a stable composition.

In addition to the above-mentioned components (a), (b) and water, known components such as builders which can be added to this type of liquid detergent composition as optional components can be added.

The builder has the effect of dispersing the solid particle soil from the clothing into the washing bath and the effect of preventing the particles from re-adhering (recontaminating) to the clothing, and is preferably incorporated in the present invention. By blending an oligomer of a specific molecular weight as a builder,
Detergency is further improved.

The oligomer has an average molecular weight of 500 to
A polycarboxylic acid type oligomer (hereinafter simply referred to as an oligomer) having a molecular weight of 100,000, preferably 1000 to 10000, and a part of which may be in the form of a salt. Maleic acid and an olefin having 1 to 8 carbon atoms, acrylic acid, methacrylic acid, itaconic acid And a salt of a copolymerized oligomer with a copolymerizable monomer such as methacrylsulfonic acid, and / or a salt of a single oligomer such as acrylic acid, methacrylic acid, and maleic acid. In particular, when the oligomer represented by the following formula (V) or / and the oligomer represented by the following formula (VI) is used in combination with the cleaning composition of the present invention, excellent performance is exhibited. Was found.

[0036]

Embedded image

Wherein Z is an olefin having 1 to 8 carbon atoms;
Maleic acid (anhydride) such as acrylic acid, methacrylic acid, itaconic acid, and methacrylsulfonic acid, or a salt of a copolymer of maleic acid and a monomer copolymerizable with maleic acid salt, and m is a copolymer having a molecular weight of several hundreds. It is a value indicating ~ 100,000. M is _{Na, K, NH 4, H} . )

[0038]

Embedded image

(In the formula, P is a monomer capable of being homopolymerized, and examples thereof include acrylic acid, methacrylic acid, and maleic acid. L is a value such that the molecular weight of the homopolymer is several hundred to 100,000. The homopolymer is a salt of Na, K and NH _4. ) The amount of the oligomer of the formula (V) and / or the oligomer of the formula (VI) is 100 parts by weight of the surfactant (b) in the detergent composition. 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Among these oligomers, polyacrylates (Na,
K and NH ₄ ) are particularly excellent. The average molecular weight of the oligomer is
500 to 30000, especially 1000 to 10000 are suitable. When the average molecular weight exceeds 30,000, the liquid stability decreases. If it is less than 500, no sufficient improvement in the effect can be seen.

The average molecular weight of the oligomer is obtained by measuring the molecular weight distribution by measuring the solution fractionated by GPC with light scattering intensity and refractive index difference using polyethylene glycol as a standard, and then calculating the weight average molecular weight. It was obtained by

Further, as an optional component, a component which is conventionally known to be added to a detergent can be added. As such optional components, anti-staining agents such as polyacrylic acid, polyethylene glycol and carboxymethyl cellulose; anti-transfer agents such as polyvinyl pyrrolidone; metal scavengers such as citric acid, diglycolic acid, phosphoric acid or salts thereof; Alkaline agents such as alkali metal carbonates, alkali metal silicates or alkanolamines (other p
H regulator); enzymes such as protease, cellulase, amylase and lipase; enzyme stabilizers such as calcium chloride, formic acid and boric acid; lower alcohols such as ethanol; benzenesulfonic acid salts, p-toluenesulfonic acid Lower alkylbenzene sulfonates such as propylene glycol and polypropylene glycol; solubilizers such as benzoate and urea; antioxidants such as butylhydroxytoluene, distyrenated cresol and sulfite; other fluorescent dyes and blue Flavoring agents, fragrances, and antibacterial agents are included.

The concentration of the detergent composition of the present invention when washing is usually carried out using a washing machine is preferably 0.067 to 0.167% by weight, and particularly, the concentration of the surfactant in the washing liquid is 0.02 to 0.16%.
Preferably, it is added so as to be 0.06% by weight. In addition, normal washing may be performed after hand washing and soaking for a while, and the detergent concentration in that case may be higher than that in normal washing, and specifically, 1.5 to 1.5 times in normal washing.
The concentration may be tripled.

Since the liquid detergent composition of the present invention is intended for clothing which is vulnerable to alkalis or acids such as wool, it is preferably a neutral liquid detergent composition having a pH of 6 to 8.

[0044]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Liquid detergents shown in Tables 1 and 2 were prepared. In addition, liquid detergent
The pH was adjusted to 7.0 using sodium hydroxide and hydrochloric acid. The following evaluation was performed using the obtained liquid detergent. The results are shown in Tables 1 and 2.

(1) Evaluation of permeability [Preparation of test piece] A wool jersey knit cloth was 2.0 cm × 2.
It was cut to 0 cm and used as a wool specimen. [Preparation of Hard Water] The following water was used as the water for the test of permeability. Weigh 105 mg of calcium chloride (dihydrate) and dissolve in distilled water to make 1000 ml of hard water. A large amount of this hard water was made and subjected to the following tests.

[Preparation of Detergent Solution for Evaluation] 1.333 g of the liquid detergent compositions of the present invention and comparative products shown in Tables 1 and 2 were weighed and dissolved in the above hard water to prepare 1,000 ml of a solution.
These detergent aqueous solutions for evaluation are 10.5cm in diameter and about 14.5cm in height.
In a 1 liter beaker. The temperature of the solution is
The temperature was controlled at 20 ° C. (Evaluation method) The above wool test piece was gently placed horizontally on the surface of the detergent liquid for evaluation, and the time from the moment of contact with water until the wool test piece separated from the water surface and entered the water was measured. The penetration time was taken. The measurement was performed five times, and the average value was adopted. (Evaluation criteria) ○: Penetration time less than 60 seconds (good permeability) △: Penetration time 60 seconds or more and less than 100 seconds (slightly poor penetration) ×: Penetration time 100 seconds or more (poor permeability)

(2) Evaluation of Detergency The detergency of the liquid detergent compositions shown in Tables 1 and 2 was evaluated by the following method. [Preparation of artificially contaminated cloth] Using the following AE dirt components,
An artificial soil solution was prepared. (Soil component) The amount of component B was adjusted so that the total of components A, B, C, D, and E became 100%. In addition, each% is a ratio in the final dirt component. A component: 0.44% lauric acid, 3.15% myristic acid, 2.35% pentadecanoic acid, 6.31% palmitic acid, 0.44% heptadecanoic acid, 1.60% stearic acid, 7.91% oleic acid
13.33% triolein, n-hexadecyl palmitate
A mixture of 2.22% and squalene 6.66% B component: Hard water as described above C component: Egg white lecithin liquid crystal 1.98% [11.37 g of arginine hydrochloride, 4.20 g of histidine, 2.20 g of serine in 80 ml of distilled water.
After dissolving 44 g and adjusting the pH to 5.0 with concentrated hydrochloric acid, this solution and egg white lecithin were sufficiently mixed with a mixer to obtain an egg white lecithin liquid crystal. D component: Kanuma red clay 8.11% [Kanuma red clay was dried at 105 ° C for 5 hours, pulverized with an attritor, and the product passed through 150 mesh was used as mud. E component: carbon black 0.025% (Preparation of artificial soil liquid) Mix all A components, mix at 80 ° C while heating until a uniform solution is obtained, and then heat C component to 70 ° C. While stirring, the mixture was dissolved by stirring, and the component E was further added, and the mixture was stirred and uniformly dispersed. Further, the B component and the D component heated to 70 ° C. are added, and the mixture is sufficiently mixed at 70 ° C. using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., model M2-2.5). Liquid. (Preparation of Artificially Contaminated Cloth) A gravure type contaminating machine disclosed in JP-A-7-270395 was used for adhering the artificially soiled liquid to the cloth. The preparation conditions were as follows: gravure roll cell capacity: 58 cm ³ / m ² , coating speed: 1.0 m / min, drying temperature: 100 ° C., drying time: 1 minute. The cloth used was a wool muslin cloth.

[Washing Conditions and Evaluation Method] Five artificially stained cloths of 5 cm × 5 cm were placed in 1 liter of the aqueous detergent solution for evaluation, and washed with a tergotometer at 50 rpm under the following conditions. (Washing conditions) Washing time 10 minutes Detergent concentration 0.133 wt% Water hardness 4 ° DH Water temperature 20 ° C. Rinse with tap water for 5 minutes * Detergency is 550 of the original cloth before and after cleaning.
The reflectance at nm is measured using a spectral colorimeter (Model N-30 manufactured by Nippon Denshoku)
0A) and the cleaning rate (%) was determined by the following equation. Tables 1 and 2 show the measured average values of five sheets.

[0050]

(Equation 4)

(3) Evaluation of texture Processing method Fully automatic washing machine (manufactured by Matsushita Electric Industrial Co., Ltd .; NA-F60)
K2) and a commercially available sweater [UNITED COLORS OF B
Made by ENETTON (Italy), L size for women, 100 wool
%, Product number 1002D1022], and washed in a hand-washing course. The detergent concentration was 0.133% by weight, and water having a water temperature of 20 ° C. and a hardness of 4 ° DH was used. After washing, drying was performed by flat drying. The above process was repeated five times. Also,
The same applies to a commercially available acrylic sweater (acrylic 70%, wool 30%, ladies 'M size) and a commercially available polyester blouse (polyester 100%, ladies' free size). One sheet was placed in one bath and treated according to the above.

Evaluation method The sweater treated by the above method was left in a thermo-hygrostat at 20 ° C. and 65% Rh for 24 hours. About these sweaters,
Sensory evaluation was performed on the skin texture. The sensory evaluation was evaluated as an average score of five panelists according to the following criteria in comparison with the commercially available light liquid detergent Akron (registered trademark). Very excellent +2 points Good +1 point Equal 0 points Inferior -1 point Obviously inferior -2 points.

(4) Evaluation of dimensional stability Treatment method Commercial sweater (100% wool) The treatment is repeated 5 times in the same manner as in the evaluation of the texture. Evaluation method After the sweater before washing is conditioned at 20 ° C and 65% RH for 12 hours or more, sleeve length, shoulder width, body width, total length and hem width are measured, and this length is used as the original length. After the treatment, the sweater was left in a constant temperature and humidity room at 20 ° C. and 65% RH for 24 hours. Measure the same section (sleeve length, shoulder width, body width, total length, hem width) as measured before washing.

[0054]

(Equation 5)

The average value of the shrinkage rates at five locations was determined, and the average value was used as a representative value of the entire shrinkage value.

(5) Evaluation of storage stability The components shown in Tables 1 and 2 were mixed by a batch method to prepare a liquid detergent having a pH of 7.0. Each of the obtained liquid detergents was evaluated for storage stability as described below. <Storage stability> The sample was transferred to a screw tube (diameter 4 cm, height 10
cm), and stored at 50 ° C., 40 ° C., room temperature, 5 ° C., and −5 ° C., respectively. Twenty days after each storage, the presence or absence of consolidation, separation, and precipitation was visually determined, and the following evaluation was performed. . ：: Uniform and transparent liquid. X: An opaque liquid or solidification, separation or precipitation occurred.

[0057]

[Table 1]

[0058]

[Table 2]

(Note) Comparative product 15 is ES (14) [alkyl (C
₁₂ ) 10% by weight of sodium ether sulfate Na, average number of moles of added ethylene oxide 4] was 10% by weight.
S (15) [alkyl (C ₁₂ ~C ₁₃₎₎ benzenesulfonic acid Na]
Of 10% by weight. (B) in comparative products 15 and 16
The / (a) weight ratio is calculated by including ES (14) or LAS (15) in the component (b). * Silicone (1) is a compound having the following structure in the general formula (I). R: CH ₃ R ¹ : CH ₃ A: (A)-(CH ₂ ) ₃ -NH-CO-CH ₂ -O- (CH ₂ CH ₂ O) ₅ -C ₁₂ H ₂₅ and (B)-( CH ₂ ) ₃ —NH ₂ mixture [(a) / (b) = 7/3
(Molar ratio)] B:-(CH ₂ ) ₃ -O- (CH ₂ CH ₂ O) ₁₀ -CH ₃ l: 300 m: 7 n: 4 * Silicone (2) has the structure in general formula (I) Are the following compounds. R: CH ₃ R ¹ : CH ₃ A:-(CH ₂ ) ₃ -NH-CO-CH ₂ -O- (CH ₂ CH ₂ O) ₅ -C ₁₂ H ₂₅ B: -CH ₃ l: 300 m: 7n: 4 * Silicone (3) is a compound having the following structure in general formula (I). R: CH ₃ R ¹ : CH ₃ A: (a)-(CH ₂ ) ₃ -NH-CO-CH ₂ -O- (CH ₂ CH ₂ O) ₅ -C ₁₂ H ₂₅ and (d)-( CH ₂ ) ₃ -NH-CO-CH ₂ -O- (CH ₂ CH ₂ O) ₅ -C ₁₄ H
₂₉ [(a) / (d) = 7/3 (molar ratio)] B:-(CH ₂ ) ₃ -O- (CH ₂ CH ₂ O) ₁₀ -CH ₃ l: 200 m: 14 n: 8

[0060]

(Equation 6)

* PA (11): polyacrylic acid sodium salt (Mw 3,00
0) * PM (12): Na salt of pentene / maleic acid (50/50 molar ratio) copolymer (Mw 7,000) * DM (13): Na salt of diisobutylene / maleic acid (50/50 molar ratio) copolymer (Mw7,000)

[0062]

(Equation 7)

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁶ identification code FI C11D 1: 722 3:37 3:20) (56) References JP-A-5-239493 (JP, A) JP-A-7- 62387 (JP, A) JP-A-6-256793 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 3/37 C11D 10/02 C11D 17/08

Claims (3)

(57) [Claims] (1) 0.05 to 5% by weight of an amino-modified silicone derivative represented by the following general formula (I) and (b) 95 to 75% by weight of the following nonionic surfactant (i), Surfactant 5 containing 5 to 15% by weight of surfactant (ii)
And the weight ratio of (a) :( b) is (a):
(b) = 1: 100 to 1: 5. A liquid detergent composition, characterized in that: Embedded image (Where l is 100 to 600, and m and n are l: m = 100: 1 to 1)
0: 1, and m: n = 1: 10 to 10: 1. R: an alkyl group having 1 to 4 carbon atoms, a hydroxy group or an alkoxy group R ¹ ; an alkyl group having 1 to 4 carbon atoms, which may be different from each other. A: A group represented by the following (A) or a group represented by the (A) and (B), and in the latter case, the ratio of (B) in A is 50
Mol% or less. Embedded image a; 2 to 6 R ² ; a hydrogen atom or an alkyl group having 1 to 4 carbon atoms p; 1 to 6 q; 1 to 20 r; 0 to 20 R ³ ; an alkyl group B having 1 to 18 carbon atoms; alkyl group having 1 to 10 carbon atoms _{x;; - 2) a -O-} (C 2 H 4 O) x (C 3 H 6 O) y -R 4 or R ¹ R ⁴ 1~20 y; 0~20 Is shown. <Nonionic surfactant (i)> Nonionic surfactant represented by the following general formula (i): R ₁ O (R ₂ O) _n R ₃ (i) (wherein R ₁ is a linear or A branched chain alkyl group or alkenyl group having 8 to 18 carbon atoms, or an alkylphenyl group having 12 to 22 carbon atoms, R ₂ represents an alkylene group having 2 to 4 carbon atoms, R ₃ represents hydrogen or a methyl group; Or an ethyl group.
n is the number of moles of alkylene oxide added so that the HLB value of (i) is 12 to 15. <Nonionic surfactant (ii)> A compound represented by the following general formula (ii), having an HLB value of 7 to 10, and having a content of a compound of n = 0 of 4% by weight or less and having the highest content. average carbon in addition molar n _max is a nonionic surfactant R ₄ O satisfying the following formula _{(a) (CH 2 CH 2} O) n R 5 (ii) ( wherein, R ₄ is a straight chain or branched chain Represents an alkyl group or alkenyl group having 8 to 18 carbon atoms or an alkylphenyl group having 12 to 22 carbon atoms, wherein R ₅ is hydrogen or methyl, and n is selected so that the HLB value of (ii) becomes 7 to 10. It is the number of moles of ethylene oxide added.) 2. The method according to claim 2, wherein 100 parts by weight of the surfactant (b) is used.
2. The liquid detergent composition according to claim 1, comprising 0.1 to 10 parts by weight of a polycarboxylic acid type oligomer having an average molecular weight of 500 to 100,000 and a part of which may be in the form of a salt. 3. The liquid detergent composition according to claim 1, which contains water as a main medium and has a pH of 6 to 8.