JP3426322B2 - 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 detergent composition which is excellent in stability over time, has good foaming properties, is non-greasy, has an excellent conditioning effect, and is suitable for cleaning hair and the like.

[0002]

2. Description of the Related Art Conventionally, various cleansing compositions for hair and the like have been developed, and in particular, many cleansing agents such as shampoo for imparting a conditioning effect to hair have been developed.
For example, there is known a hair cosmetic in which lubricity and water repellency are increased by adding silicone as an agent for imparting a conditioning effect to improve the usability (US Pat. Nos. 2,826,551 and 3,964,500).
Etc.). However, even if silicone is dispersed as an emulsion in an aqueous solution using a surfactant, these easily separate and lack stability, and this separation is remarkable especially when a large amount is added to obtain a conditioning effect. Becomes

Further, hair cosmetics in which high-viscosity silicone is dispersed with a surfactant to impart a conditioning effect are known (Japanese Patent Laid-Open Nos. 61-21022, 64-13012, and 64-13013). No. However, such a hair cosmetic composition has a problem in that when continuously used, high-viscosity silicone adheres and accumulates on the hair to give a sticky feeling or a heavy oily feeling, and the cohesion of the hair is deteriorated.

Further, hair cosmetics such as a set lotion, a hair spray and a hair styling agent, which form a film having a good setting property on the hair surface by blending a silicone resin and a silicone oil, are known (JP-A-61-161). 164214, 63-313713, and JP-A-1-165509). However, these are essentially hair setting agents and are used in the state of being dissolved in a solvent in order to form a silicone resin film on the hair. Therefore,
When these solvent-soluble silicone resins are blended with shampoo or the like, there are problems that a sticky feeling is generated or stability with time is impaired.

Also known is a skin cosmetic in which a mixture of hydrophobic powder such as silicone resin and an oil agent such as silicone oil is dispersed in an aqueous phase using a cross-linked polyacrylic polymer compound. (JP-A-2-19310, etc.). However, this cosmetic composition improves the feeling of use when used as a foundation, and does not improve the feeling of use on hair.

Further, silica hair particles are blended to impart flexibility, smoothness and anti-static property, and there is no sticky feeling, and a hair rinse agent which easily retains a hairstyle (JP-A-57-14).
No. 0708), and a hair styling agent containing a fine particle powder such as silica, which does not have a sticky feeling, can impart a dry feeling, and has excellent setting power (Japanese Patent Laid-Open No. 4-124121).
No. publication) is known. However, hair cosmetics using these silica particles are formulated as a rinsing agent or a spray type hair styling agent, and increase the viscosity or shake at the time of use to maintain the uniformity of the silica particles.
Therefore, when it is applied to a low-viscosity detergent such as shampoo, there is a problem that formulation is difficult due to problems such as separation.

Furthermore, when these are compounded in a surfactant in order to utilize the characteristics of the above-mentioned silicone and silica particles, they have a defoaming action (Silicone Handbook, pages 216 to 220, Kunio Ito). , Nikkan Kogyo Shimbun Co., Ltd., 1990), there is a problem that the foaming which is satisfactory as a cleaning agent cannot be obtained.

[0008]

Therefore, the object of the present invention is to solve the above-mentioned various problems, in which the silicone component is stably dispersed in the surfactant, the foaming is good, and there is no sticky feeling after drying. Another object of the present invention is to provide a detergent composition which is excellent in usability and conditioning effect.

[0009]

Under such circumstances, as a result of intensive studies by the present inventors, as a result of dispersing a mixture of silica particles, a water-soluble silicone derivative and dimethylpolysiloxane in a surfactant aqueous solution, The inventors have found that a detergent composition having excellent stability over time, good foaming, non-greasiness, and excellent conditioning effect can be obtained, and the present invention has been completed.

That is, the present invention relates to (A) silica particles,
(B) The following formula (1), (2) or (3);

[Chemical 5] [Wherein R ¹ is the following formula (4);

[Chemical 6] (In the formula, R ² represents a divalent hydrocarbon group, and c is 0 or 1
, D is an integer of 1 to 5, and e is the formula (1),
The weight of the alkylene oxide group (C _d H _2d O) _e in (2) or (3)
The amount is 40% by weight or more) or the following formula (5);

[Chemical 7] (In the formula, R ² and c have the same meanings as described above, and f is 0 to
Represents an integer of 10), and a and b are flat.
It shows the number at which the average molecular weight is 2000 to 100,000. Was
However, alkylene oxide in formula (1), (2) or (3)
The weight of the group (C _d H _2d O) _e is 40% by weight or more. ]]
The present invention provides a detergent composition comprising a mixture of the water-soluble silicone derivative (C) and dimethylpolysiloxane (C) dispersed in an aqueous surfactant solution.

Among the components (A) used in the present invention, the silica particles have the following formula:

[0012]

[Chemical 5]

Amorphous silicon dioxide having a three-dimensionally cross-linked network structure with a siloxane bond is preferable. These are white, odorless particles that have a structure in which the molecular surface is covered with silanol groups, are hydrophilic, and are chemically stable. Further, in the present invention, it is also possible to use hydrophobic silica particles obtained by surface-treating such silanol groups on the surface of amorphous silicon dioxide with methyl hydrogen silicone or the like.

Since the stability of these silica particles with time decreases as the average particle size decreases, those having an average particle size of 0.01 to 500 μm are preferable. Especially preferred is 1 to 10 μm. The shape of these silica particles is not particularly limited, but is preferably spherical for improving the feeling of use.

As such silica particles, commercially available products such as Sildex (manufactured by Asahi Glass Co., Ltd.), S-Quartz (manufactured by Nippon Steel Chemical Co., Ltd.) and Admafine (manufactured by Admax Co.) can be used.

[0016]

[0017]

The water-soluble silicone derivative of the component (B) used in the present invention is represented by the following formula (1), (2) or (3).

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

In the water-soluble silicone derivative represented by the formulas (1), (2) and (3), the divalent carbonization represented by R ² in the group represented by the formula (4) represented by R ¹ As hydrogen,
Methylene group, ethylene group, propylene group, butylene group,
-CH ₂ CH (CH ₃ ) CH ₂ -and other branched alkylene groups,-(CH
₂ ) An aryl alkylene group such as _2- C ₆ H ₄ and the like can be mentioned. Of these, an alkylene group, particularly a propylene group is preferable. Further, c is preferably 1 and d is preferably 2 or 3. Here, e-C _d H _2d O- may have 2 or 3 of d bonded in a block or random manner. In addition,
An alkylene oxide group (C _d H in the formula (1), (2) or (3)
The weight of _2d O) _e needs to be 40% by weight or more in order to enhance the water solubility of the silicone derivative.
It is preferably 90 to 90% by weight, more preferably 60 to 80% by weight. In addition, in the group represented by the formula (5) represented by R ¹ , c is preferably 1 and f is preferably an integer of 2 to 4.

Examples of such water-soluble silicone derivatives include KF351A, KF353A and KF354.
A, KF355A (above, Shin-Etsu Chemical Co., Ltd.), SH3
771, SH3794 (above, Toray Dow Corning
Commercial products such as Silicone Co., Ltd.) can be used.

The component (C) dimethylpolysiloxane used in the present invention has, for example, the following formula:

[0028]

[Chemical 9]

(In the formula, n represents a number of 0 to 20000)
Can be mentioned. Where n in the formula
It is preferably 350 to 2500.

The mixing ratio of the components (A), (B) and (C) is 1: 1: 1000 to 90: 90: 100 (weight ratio).
Is preferable, and 5: 1: 96 to 5:10:85 is particularly preferable from the viewpoint of stability of the composition.

The total content of the components (A), (B) and (C) is preferably 0.1 to 10.0% by weight based on the total composition, and especially 1 to 3% by weight is dried. It is preferable because the subsequent hair has good slipperiness and a particularly smooth feeling is obtained.

The surfactant used in the present invention may be any of anionic, amphoteric and nonionic surfactants, and examples thereof include the following.

Anionic surfactant: (1) A linear or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16. (2) Having a linear or branched alkyl group or alkenyl group having an average carbon number of 10 to 20 and having an average of 0.5 to 8 in one molecule.
Having moles of ethylene oxide, propylene oxide, butylene oxide, added ethylene oxide and propylene oxide in a ratio of 0.1 / 9.9 to 9.9 / 0.1 or ethylene oxide and butylene oxide of 0.1.
Alkyl or alkenyl ether sulphate added at a ratio of /9.9 to 9.9 / 0.1. (3) An alkyl or alkenyl sulfate having an alkyl group or an alkenyl group having an average carbon number of 10 to 20. (4) An olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. (5) An alkane sulfonate having an average of 10 to 20 carbon atoms in one molecule. (6) A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule. (7) It has an alkyl group or an alkenyl group having an average carbon number of 10 to 20, and has an average of 0.5 to 8 mol of ethylene oxide, propylene oxide or butylene oxide in one molecule, or ethylene oxide and propylene oxide have an average molecular weight of 0.
Ethylene oxide and butylene oxide added in a ratio of 1 / 9.9 to 9.9 / 0.1 or 0.1 / 9.9 to 9.
Alkyl or alkenyl ether carboxylates added in the ratio 9 / 0.1. (8) An α-sulfofatty acid salt or ester having an alkyl group or an alkenyl group having an average of 10 to 20 carbon atoms. (9) An N-acyl amino acid type surfactant having an acyl group having 8 to 24 carbon atoms and a free carboxylic acid residue. (10) A phosphoric acid mono- or diester type surfactant having an alkyl group or an alkenyl group having 8 to 24 carbon atoms. (11) Polyoxyethylene alkylsulfosuccinic acid monoester salt having an alkyl group having 8 to 16 carbon atoms.

Amphoteric surfactant: (12) α-position addition type secondary amide type or tertiary amide type imidazoline type amphoteric surfactant having an alkyl group, an alkenyl group or an acyl group having 8 to 24 carbon atoms. (13) Carbobetaine-based, amidobetaine-based, sulfobetaine-based, hydroxysulfobetaine-based or amidosulfobetaine-based amphoteric surfactants having an alkyl group, an alkenyl group, or an acyl group having 8 to 24 carbon atoms.

Nonionic surfactant: (14) Higher fatty acid alkanolamide or alkylene oxide adduct having a long-chain acyl group having 10 to 20 carbon atoms. (15) General formula; R ³ -O- (R ⁴ O) _t (G) _u (In the formula, R ³ represents a linear or branched alkylene group or alkenyl group having 6 to 18 carbon atoms, and R ⁴ Has 2 to 4 carbon atoms
Alkyl glycoside-based surfactant represented by the formula (3), G represents a reducing sugar having 5 to 6 carbon atoms, t represents 0 to 10 and u represents 1 to 10.

Among these surfactants, (2) alkyl ether sulfate, (3) alkyl sulfate, (10) long-chain alkyl phosphate monoester salt, (11) sulfosuccinic acid monoester salt and the like are anionic. Surfactant, (1
2) Amphoteric surfactants such as imidazoline-based amphoteric surfactants, and (15) nonionic surfactants such as alkylglycoside-based surfactants are preferable.

These surfactants may be used either individually or in combination of two or more. When they are added in an amount of 5 to 30% by weight, especially 10 to 20% by weight in the total composition, they have particularly good foaming and are not sticky. Moreover, it is preferable because it has an excellent conditioning effect.

The balance is water, and it is preferably added in an amount of usually 50 to 90% by weight, particularly 60 to 80% by weight, based on the total composition.

In the detergent composition of the present invention, in addition to the above-mentioned components, if necessary, a component usually used for a detergent such as shampoo, for example, a suspending agent such as ethylene glycol distearate or ethylene glycol monostearate. , Dissolution agents such as propylene glycol and glycerin, ethanol, inorganic salts, higher alcohols, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, viscosity modifiers such as natural polymers, methylphenyl polysiloxane, low HLB
Polyether-modified silicones, amino-modified silicones, fatty acid-modified silicones, fluorine-modified silicones, cyclic silicones, alkyl-modified silicones, alcohol-modified silicones, and other silicone derivatives other than component (B), fragrances, colorants, UV absorbers, antioxidants Agents, anti-dandruff agents, bactericides, preservatives, pH adjusting agents and the like can be appropriately added within a range that does not impair the effects of the present invention.

The detergent composition of the present invention is prepared, for example, by first thoroughly mixing the components (A), (B) and (C) and then dispersing them with a surfactant, and then preparing the dispersion. It can be produced by adding and dispersing it in an aqueous solution containing a surfactant and other components.

The detergent composition of the present invention thus obtained is
It is preferably used for hair shampoo, body shampoo and the like.

[0042]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The following test methods for stability over time, lathering, stickiness, finger-holding property, and smoothness are as follows.

(Aged stability) The floating of components (B) and (C) was measured from above when the cleaning composition was put into a storage bottle having a height of 10 cm to a height of 9 cm and stored at 50 ° C. for 10 days. Then
The following criteria evaluated. ⊚: 0 mm float from the top or 0 mm sediment from the bottom; excellent stability over time. ◯: Float less than 3 mm from the top or sedimentation less than 3 mm from the bottom;
Slightly superior in stability over time. Δ: 3 mm or more floating from the top or 3 mm or more sedimentation from the bottom;
The stability over time is poor.

(Foaming) A cylinder containing the detergent composition 0.
Add 5g, lanolin 0.3g and 4 ° hard water 9.2g,
Further, 90 g of 4 ° hard water was poured from the upper portion and the mixture was foamed. The volume of the foam was measured after 10 seconds (foaming force), and after 120 seconds, the volume of the foam was measured (foam stability), and evaluated according to the following criteria. Measured value after 10 seconds (foaming power): A: Very good foaming power (150 ml or more). ◯: Foaming power is rather good (100 to 150 ml). B: Poor foaming power (less than 100 ml). Measured value after 120 seconds (foam stability): A: Foam stability is very good (130 ml or more). ◯: Foam stability is rather good (80 to 130 ml). B: Poor foam stability (less than 80 ml).

(Stickiness and finger-likeness during washing and drying of hair) 20 g of hair of a healthy Japanese woman (length 15
cm), and 1 g of the detergent composition was applied to this hair bundle, and the mixture was bubbled for 1 minute and then rinsed with running water for 30 seconds. next,
It was towel-dried and further dried with a drier, and the dry sticky feeling, finger-holding feeling and dry feeling were evaluated according to the following criteria. Stickiness and good finger feel: ◎: Not sticky, and the finger feels smooth. ○: Slightly sticky, and the fingering is good. Δ: Sticky, and fingering was poor. Smoothness: ◎: A slippery feeling is imparted to the hair, which is very smooth. ◯: A little slippery feeling is given to the hair, and it is slightly silky. Δ: The hair has no slippery feeling and does not dry.

Example 1 A detergent composition having the following composition was produced by the following production method. First, the components (A), (B) and (C) were thoroughly mixed and then emulsified and dispersed with a part of the surfactant. Next, the rest of the surfactant, water and other components were mixed to obtain a detergent composition.

[0047]

[Table 1] (Component) (% by weight) Polyoxyethylene (EO 3) lauryl ether Sodium sulfate 16 Silica powder (S-quartz M-1, particle size 1.0 μm) 0.5 Water-soluble silicone derivative (KF351A) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.0 Preservatives, colorants, fragrances Water balance

Example 2 By the same production method as in Example 1, a cleaning composition having the following composition was produced.

[Table 2] (Component) (% by weight) Polyoxyethylene (EO 3) lauryl ether Sodium sulfate 16 Silica powder (Sildex L-31, particle size 3 μm) 0.5 Water-soluble silicone derivative (KF353A) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.0 Cationized cellulose (Polymer JR400) 0.4 Preservatives, colorants, fragrances Water balance

[0049]

[0050]

Example 3 A detergent composition having the following composition was produced by the same production method as in Example 1. However, Zpt was dispersed in polyvinyl alcohol and finally mixed. (Component) (% by weight) Lauryl sulfate triethanolamine 16 Silica powder (S-quartz M-0.5, particle size 0.5 μm) 0.5 Water-soluble silicone derivative (SH3749) 0.5 Dimethylpolysiloxane (viscosity 100, 000cs) 2.0 Cationized cellulose (Cathello M-80, manufactured by Kao) 0.5 Zpt (zinc pyrithione) 1.0 Polyvinyl alcohol 1.0 Preservative, colorant, fragrance Sufficient water balance amount

Example 4 A cleaning composition having the following composition was produced by the same production method as in Example 1. However, ethylene glycol monostearate as a suspending agent was added last at 60 to 70 ° C., and cooled slowly. (Component) (wt%) polyoxyethylene (EO 4) coconut oil alkylsulfo disodium disodium 10 lauryl sulfate triethanolamine 16 silica powder (Sildex L-51, particle size 5 μm) 0.5 water-soluble silicone derivative ( KF351A) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.0 Stearyl trimethyl ammonium chloride 0.5 Ethylene glycol monostearate 2.0 Lauric acid diethanolamide 2.0 Preservative, colorant, fragrance Sufficient water balance amount

[0053]

Comparative Example 1 According to the production method of Example 1, a cleaning composition having the following composition was obtained.

[Table 8] (Component) (% by weight) Polyoxyethylene (EO 3) lauryl ether Sodium sulfate 16 Silica powder (S-quartz M-1, particle size 1.0 μm) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.5 Preservatives, colorants, fragrances Water balance

Comparative Example 2 A cleaning composition having the following composition was produced according to the production method of Example 2.

[Table 9] (Component) (% by weight) Polyoxyethylene (EO 3) lauryl ether Sodium sulfate 16 Silica powder (Sildex L-31, particle size 3 μm) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.5 Cationized cellulose (Polymer JR400) 0.4 Preservatives, colorants, fragrances Water balance

Comparative Example 3 According to the production method of Example 1 , a cleaning composition having the following composition was produced. (Component) (wt%) polyoxyethylene (EO 3) lauryl ether sodium sulfate 16 solvent-insoluble silicone resin (Tospearl 130, particle size 3 μm) 0.5 dimethylpolysiloxane (viscosity 100,000 cs) 2.5 preservative, coloring Agent, fragrance Sufficient amount Water balance amount

Comparative Example 4 According to the manufacturing method of Example 1 , a cleaning composition having the following composition was manufactured. (Component) (% by weight) N-lauroyl-N-carboxymethyl- (2-hydroxyethyl) ethylenediamine sodium 16 Solvent-insoluble silicone resin (Tospearl 120, particle diameter 2 μm) 0.5 Dimethylpolysiloxane (viscosity 100,000 cs) 2 .5 Marquat 550 0.5 Preservative, colorant, fragrance Sufficient water Balance amount

Comparative Example 5 A cleaning composition having the following composition was produced according to the production method of Example 3 . (Component) (% by weight) Lauryl sulfate triethanolamine 16 Silica powder (S-quartz M-0.5, particle diameter 0.5 μm) 0.5 Dimethyl polysiloxane (viscosity 100,000 cs) 2.5 Cationized cellulose (catissero) M-80, manufactured by Kao) 0.5 Zpt (zinc pyrithione) 1.0 Polyvinyl alcohol 1.0 Preservative, colorant, fragrance Sufficient water balance amount

Comparative Example 6 According to the manufacturing method of Example 4 , a cleaning composition having the following composition was manufactured. (Component) (wt%) polyoxyethylene (EO 4) coconut oil alkylsulfo disodium disodium 10 lauryl sulfate triethanolamine 16 silica powder (Sildex L-51, particle size 5 μm) 0.5 dimethylpolysiloxane (viscosity 100,000 cs) 2.5 Stearyl trimethyl ammonium chloride 0.5 Ethylene glycol monostearate 2.0 Lauric acid diethanolamide 2.0 Preservative, colorant, fragrance Sufficient water balance amount

Comparative Example 7 A cleaning composition having the following composition was produced according to the production method of Example 1 . (Component) (% by weight) Lauryl sulfate triethanolamine 16 Solvent-insoluble silicone resin (KMP590) 0.5 Dimethylpolysiloxane (viscosity 100,000 cs) 2.5 Octopirox 0.5 Preservative, colorant, fragrance sufficient amount Water balance

Test Example 1 Using the detergent compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 7, stability over time, lathering (foaming power, lather stability), sticky feeling and finger-holding property. , Tested for a dry feel. The results are shown in Tables 15 and 16.

[0062]

[Table 1]

[0063]

[Table 16]

As is clear from Tables 15 and 16, the cleaning compositions of Examples 1 to 4 were excellent in each test item. On the other hand, the compositions of Comparative Examples 1 to 7 containing no water-soluble silicone derivative were particularly inferior in foaming (foaming power, foam stability).

[0065]

The detergent composition of the present invention is excellent in stability over time and is also excellent in foaming (foaming power, foam stability). In addition, it has no sticky feeling, can be easily touched with fingers, can give a silky feeling, and has an excellent conditioning effect. The cleansing composition of the present invention can be suitably used as a cleansing agent for cleaning hair and body.

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-310539 (JP, A) JP-A-5-310540 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/00-7/50 C11D 1/00-10/06

Claims (5)

(57) [Claims] 1. (A) silica particles, (B) the following formula (1),
(2) or (3); [Wherein R ¹ is the following formula (4); (In the formula, R ² represents a divalent hydrocarbon group, and c is 0 or 1
, D is an integer of 1 to 5, and e is the formula (1),
The weight of the alkylene oxide group (C _d H _2d O) _e in (2) or (3)
The amount is 40% by weight or more) or the following formula (5); (In the formula, R ² and c have the same meanings as described above, and f is 0 to
Represents an integer of 10), and a and b are flat.
It shows the number at which the average molecular weight is 2000 to 100,000. Was
However, alkylene oxide in formula (1), (2) or (3)
The weight of the group (C _d H _2d O) _e is 40% by weight or more. Represented by]
Water-soluble silicone derivatives, and (C) mixture detergent composition characterized in that dispersed in the aqueous surfactant solution of dimethyl polysiloxanes. 2. The silica particles (A) have an average particle diameter of 0.0.
The cleaning composition according to claim 1, which has a thickness of 1 to 500 μm. 3. The dimethylpolysiloxane (C) has the following formula: The cleaning composition according to claim 1, which is represented by the formula (n represents a number of 0 to 20000). 4. The mixing ratio of the components (A), (B) and (C) is 1: 1: 1000 to 90: 90: 100 (weight ratio).
The cleaning composition according to claim 1, which is 5. A mixture containing components (A), (B) and (C) in an amount of 0.1 to 10.0% by weight in the total composition.
The cleaning composition described.