JPH07536B2 - Shamp-composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a shampoo composition containing an anion activator, and more specifically, it has excellent foam viscosity and conditioning properties, and moreover the stability of the anion activator at low temperatures is improved. It relates to a very good shampoo composition.

Problems to be Solved by Conventional Techniques and Inventions Recently, hair care behaviors have become diverse, and shampoos having various effects are commercially available due to this tendency. In this case, there are many demands from consumers for shampoo, but in addition to the basic performance of conventional shampoo such as foaming, the feel of foam during use, that is, foam characteristics such as foam viscosity, and suppleness of hair. There is a demand for additional performance, such as conditioning properties that make it easier to put together and to make it easier to put together.

Conventionally, as a surfactant for a liquid shampoo composition, an anion activator is mainly used in the form of a soda salt, an ethanolamine salt or the like. In this case, among the anion activators, α-olefin sulfonate and alkyl ethoxy sulphate are particularly preferable. Are often used.

However, these anion activators have the advantages of high foamability and high detergency, but have poor liquid stability at low temperatures, and thus have the drawback of becoming cloudy at low temperatures and reducing the commercial value. Moreover, the shampoo composition using an anion activator does not have sufficient foam viscosity and conditioning properties.

On the other hand, it is possible to use a hydrotrope agent such as ethanol, propylene glycol, or glycerin in order to improve the stability of the anion activator at low temperature, but actually, the hydrotrope agent was added to the shampoo composition. In this case, there is an effect of lowering the freezing point of water, but almost no effect of improving the low-temperature stability of the anion activator is observed, and on the contrary, the free water in the system may decrease and the precipitation of salt may increase. .

In order to improve the low temperature stability of the AOS salts, of C ₈ -C ₂₀
Combined use of an AOS salt with an alkali metal salt, an ammonium salt or an organic base of an alkyl or alkenyl polyglycol ether carboxylic acid (Japanese Patent Publication No. 47-26845), an AOS salt and a substituted fatty acid amide component, a sulfonated hydrotrope component, etc. To be used together with (Japanese Patent Publication No. 50-1127).
No. publication) is proposed. But these suggestions too
The low temperature stability of AOS salt has not been sufficiently improved.

Therefore, there is a demand for a shampoo composition which is excellent in foam viscosity at the time of washing hair, conditioning after washing, and which does not deteriorate the stability of the anion activator even at a low temperature such as winter, but is still sufficiently satisfactory. No suggestions have been made.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an anion activator-containing shampoo composition that is excellent in low-temperature stability, foam viscosity, and conditioning properties.

Means and Actions for Solving Problems That is, the present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, the anionic activator has a specific polyalkylene glycol represented by the formula (1) described later. It was found that, when used in a predetermined amount, the foam viscosity and the conditioning property of the shampoo composition are improved, and the stability of the anionic activator when stored under low temperature is significantly improved, and the present invention is completed. I arrived.

Therefore, the present invention provides a shampoo composition containing an anion activator represented by the following formula (1): (However, R ₁ is a fatty alcohol residue having 8 to 22 carbon atoms, and n is
40 to 80 mol, Y represents a linear or branched alkyl group having 8 to 22 carbon atoms. ) The polyalkylene glycol represented by
A shampoo composition comprising 0.5 to 10% by weight is provided.

In the present invention, by using the anion activator and the polyalkylene glycol of the above formula (1) in combination, the foam viscosity and the conditioning property are improved without impairing the foaming performance of the anion activator, and the low temperature of the anion activator is used. The stability is remarkably improved. In this case, by additionally using a nitrogen-containing amphoteric activator, it is possible to further improve the foam viscosity, the conditioning property, and the low-temperature stability of the anionic activator.

Hereinafter, the present invention will be described in more detail.

The shampoo composition of the present invention comprises a shampoo composition containing an anion activator and 0.5 to 10% (% by weight, the same applies hereinafter) of the total polyalkylene glycol represented by the formula (1). .

In this case, any anion activator that is usually used in the present invention can be used, and the low temperature stability of these anion activators can be improved, and the foam viscosity and conditioning property of shampoo can be improved, but it is particularly effective. As the anion activator that can be used, the following (A) to
Examples include those shown in (D), and when these activators (A) to (D) are used, the effects of the present invention are more reliably exhibited.

(A) The following formula (2) R ₂ SO ₃ M ₁ (2) (wherein R ₂ is an alpha olefin having 12 to 16 carbon atoms, a vinylidene type olefin having 12 to 16 carbon atoms, and an inner having 12 to 16 carbon atoms) An olefin, a hydroxyalkyl group having 12 to 16 carbon atoms or a linear or branched paraffin having 10 to 18 carbon atoms, M ₁ represents an alkali metal, an alkali-substituted ammonium or a hydroxyalkyl-substituted ammonium). salt.

Specific examples of the compound represented by the above formula (2) include α-
A substance called olefin sulfonate (AOS salt), which has an average carbon number of 12 to 12 usually obtained by a wax cracking method, an ethylene polymerization method using a Ziegler catalyst, or the like.
Starting from 16 α-olefins as a raw material, this is held in a thin film and sulfonated with gaseous anhydrous sulfuric acid diluted with an inert gas, then neutralized with an alkali metal salt such as sodium hydroxide or an alkaline earth metal salt. However, those obtained by hydrolysis are included. In this case, the product obtained is
For example, HOS (hydroxyalkane sulfonate) 10-4
5% by weight (however, 2HOS is 0.5 to 8% by weight, usually 1 to 5% by weight, 3HOS or more is 5 to 44.5% by weight), ANS (alkenyl sulfonate) is 55 to 80% by weight, and DS (disulfonate) is 3 It is a mixture containing about 15% by weight.

(B) The following formula (3) R ₃ R ₄ Om-OSO ₃ M ₂ (3) (wherein R ₃ is substituted with an alkyl group having 8 to 18 carbon atoms or an alkyl group having 5 to 15 carbon atoms) Alkylphenyl group, R ₄ is an alkylene group having 2 to 3 carbon atoms, m is 0 to 6 as an average value, and M ₂ is an alkali metal or an alkaline earth metal.

Specific examples of the compound represented by the above formula (3) include natural lauryl alcohol polyoxyethylene (n = 3) sulfuric acid ester, oxo process synthesized C _{11 to} C ₁₅ aliphatic alcohol polyoxyethylene (n = 3) sulfuric acid ester, Oxo method synthesis C ₁₂
~ C ₁₃ Aliphatic alcohol oxyethylene sulfate, C
Examples thereof include sulfuric acid esters of _{12 to} C ₁₃ aliphatic alcohols and those in which these sulfuric acid ester moieties have become sodium salts, potassium salts or alkanolamine salts of sulfuric acid. Of these, sodium polyoxyethylene lauryl ether sulfate (n = 3) is particularly preferably used.

(C) The following formula (4) (However, R ₅ is a non-aromatic hydrocarbon group having an average carbon number of 9 to 17,
M ₃ and M ₄ each represent an ammonium ion, an alkanolamine ion, a lower alkylamine ion, a cation of a basic amino acid, sodium, potassium, an alkaline earth metal or hydrogen. ) N-acyl glutamic acid represented by or a derivative thereof.

Specific examples of the compound of the above formula (4) or a derivative thereof include N-lauroyl glutamic acid; N-myristoyl glutamic acid; N-palmitoyl glutamic acid; low carbon number fraction and high carbon fraction of coconut oil fatty acid or hardened tallow fatty acid. And N-acyl glutamic acid synthesized from a fat solution obtained by cutting and a mixture of these N-acyl glutamic acid, and monoethanolamine salt, diethanolamine salt, triethanolamine salt of these N-acyl glutamic acid,
Examples thereof include sodium salt and potassium salt.
These may be optically active or racemic.

(D) The following formula (5) (However, R ₆ is a non-aromatic hydrocarbon group having an average carbon number of 9 to 17,
R ₇ is a linear or branched alkyl group having 1 to 4 carbon atoms, M ₅ is an ammonium ion, an alkanolamine ion, a lower alkylamine ion, a cation of a basic amino acid, sodium, potassium, an alkaline earth metal or Hydrogen and p are 1 or 2. ) An N-acyl-N-alkylamino acid represented by or a salt thereof.

As the compound of the above formula (5) or a salt thereof, specifically,
For example, N-lauroyl-N-ethylglycine, N-lauroyl-N-isopropylglycine, N-lauroylsarcosine, N-myristoylsarcosine, N-palmitoylsarcosine, N-lauroyl-N-methylbetaalanine, N-lauroyl. -N-ethyl beta alanine,
Mention may be made of N-myristoyl beta-alanine, N-palmitoyl beta-alanine, mixtures thereof and their monoethanolamine salts, diethanolamine salts, triethanolamine salts, sodium salts, potassium salts and the like.

The anionic activator may be used alone or in combination of two or more. Further, the blending amount thereof is preferably 5 to 30%, particularly 10 to 20% of the entire composition, and the blending amount within this range ensures the effects of the present invention.

In the present invention, the anion activator and the compound of the formula (1) are used in combination. In this case, the kind of the compound of the formula (1) is not particularly limited, but particularly R ₁ has 10 to 10 carbon atoms. 1
8, n of 50 to 60 moles and Y having 10 to 18 carbon atoms can be preferably used. Specifically, polyoxide decylene (1) polyoxyethylene (60) beef tallow alkyl ether, etc. can be effectively used. Can be used.

The polyalkylene glycol of the above formula (1) may be used alone or in combination of two or more. In addition, the blending amount is required to be 0.5 to 10% of the entire composition, and if it is less than 0.5%, the low temperature stability of the anion activator, the effect of improving the foam viscosity and the conditioning property are not sufficiently exhibited, On the other hand, if it exceeds 10%, the conditioning property such as sticky hair is deteriorated and the shampoo gels, so that the object of the present invention cannot be achieved. The more preferable compounding amount of the compound of the formula (1) is 3 to 10%.
Is.

In the present invention, in addition to the polyalkylene glycol of the above formula (1), a nitrogen-containing amphoteric activator may be used in combination to further improve foam viscosity, conditioning properties and low-temperature stability of the anionic activator.

In this case, the type of nitrogen-containing amphoteric activator is not limited,
In particular, the following (E) to (G) are preferably used.

(E) The following formula (6) (R ₈ is an alkyl group or alkenyl group having an average carbon number of 9 to 17, R ₉ is —CH ₂ COOM ₆ or —CH ₂ CH ₂ COOM ₆ , R ₁₀ is hydrogen,
CH ₂ COOM ₆ or -CH ₂ CH ₂ COOM ₆ is shown. Here, M ₆ is a cation that forms a water-soluble salt. ) Amidoamine type amphoteric activator represented by.

Specific examples of the compound of the above formula (6) include N-
Lauroyl-N- (2-hydroxyethyl) -N-carboxymethylethylenediamine, N-lauroyl-N-
Examples thereof include (2-hydroxyethyl) -N'-carboxyethylethylenediamine and N-lauroyl-N- (2-hydroxyethyl) -N'-N'-bis (carboxyethyl) ethylenediamine.

(F) The following formula (7) (However, R ₁₁ is an alkylphenyl group substituted with an alkyl group having an average carbon number of 7 to 19 or an alkyl group having an average carbon number of 7 to 15, R ₁₂ is an alkylene group having an average carbon number of 2 to 3, and R ₁₃ is hydrogen. , -CH ₂ COOM ₇ or -CH ₂ CH ₂ COOM ₇ , where M ₇
Represents hydrogen, sodium, potassium, alkanolamine or alkaline earth metal. ) Amidoamine type amphoteric activator represented by.

Specific examples of the compound represented by the above formula (7) include N-lauroyl-N'-carboxymethyl-N'-carboxymethoxyethylethylenediamine and N-lauroyl-N '.
-Carboxyethyl-N '-(2-hydroxyethyl)
-Ethylenediamine, N-lauroyl-N'-carboxyethoxyethylethylenediamine, N-lauroyl-
Examples thereof include N'-carboxyethyl-N'-carboxyethoxyethylethylenediamine.

(G) The following formula (8), (9) or (10), that is, (However, in the above formulas (8) to (10), R ₁₄ is an alkyl group or an alkenyl group having 5 to ₁₉ carbon atoms, and R ₁₅ is 1 carbon atom.
To 4 alkylene groups, R ₁₆ is an alkylene group having 1 to 4 carbon atoms or an alkylene group substituted with an OH group, M ₈ and M ₉ are cations derived from hydrogen, an alkali metal or an alkanolamine, and G is an anion. Is. ) An imidazolinium betaine-type or sulfobetaine-type amphoteric active agent represented by: In this case, among these (8)
Alternatively, it is particularly preferable to use the compound represented by the formula (9).

As the compound of the above formula (8) or (9), specifically, for example, the following formulas (11) to (16), that is, And the like.

Further, as the compound of the above formula (10), specifically, for example, the following formulas (17) to (18), that is, And the like.

The nitrogen-containing amphoteric activator may be used alone or in combination of two or more, and the compounding amount thereof is preferably 1 to 5% of the total composition. %
If it exceeds, the shampoo may gel.

The shampoo composition of the present invention may contain, if necessary, auxiliary additives generally used in the prior art, as long as the effects of the present invention are not affected by the purpose of use and the like. Such additives include, for example, salt, mirabilite, solubilizer, BT
H, antioxidants such as α-tocopherol, ultraviolet absorbers, protein derivatives, animal extract, fungicides, pigments,
Examples include fragrances and conditioning agents for cationic polymers.

Further, there is no problem in adding an appropriate amount of other kinds of surfactants such as nonionic surfactants and amphoteric surfactants other than those mentioned above for the purpose of adjusting detergency and foaming. In this case, examples of these other types of surfactants include polyoxyethylene higher alcohol phosphates or salts thereof, polyoxyethylene higher fatty acid esters or salts thereof, and the like. Further, as the thickener, those which have been conventionally used can be added. For example, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, polyethylene glycol and the like can be appropriately used.

EFFECTS OF THE INVENTION As described above, the shampoo composition according to the present invention not only has excellent detergency generally required for shampoos, but also has poor low-temperature stability that shampoos containing conventional anion activators are inferior. The foam viscosity and conditioning properties are significantly improved by the blending of a specific polyalkylene glycol, and therefore there is no inconvenience that it becomes cloudy at low temperatures such as winter and reduces the commercial value, and the needs of diversified consumers It can fully meet the needs of the barber and beauty industries.

Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited to these Examples. Prior to the description of each example, the evaluation method adopted in each example will be described.

Low temperature stability Samples stored in a transparent container are stored at -5 ° C for 1 hour in a constant temperature bath.
The sample was stored for a month, and the appearance of the sample was visually observed to evaluate the low temperature stability according to the following criteria.

◯: Uniformly transparent Δ: Slight precipitation precipitation ×: Significant precipitation precipitation Conditioning property A comprehensive evaluation of three points: static friction coefficient, smoothness of hair, and non-stickiness during rinsing. Each evaluation method is as follows. Is the street.

(1) Static friction coefficient Hair (5 g, 20 cm) was washed with 1.0 g of sample shampoo for 1 minute, and rinsed in a thermostatic chamber at a temperature of 25 ° C and a relative humidity of 65%.
It was left to stand for a time to dry. After drying, the static friction coefficient was measured using a friction coefficient meter (manufactured by Shinko Electric Co., Ltd.). From the comparison with the smoothness of the hair by the sensory test, the smoothness of the hair can be detected when the coefficient of static friction is 0.17 or less.

(2) Smoothness of hair This is a sensory evaluation method, and the smoothness of the hair bundle (5 g, 20 cm) after washing, rinsing and drying is
Evaluation was carried out by 20 testers by a paired comparison method in which a commercial shampoo was used as a control.

Evaluation criteria ◎: Smoothness is superior to commercial products ○: 〃 Slightly excellent △: 〃 Equivalent ×: 〃 Inferior (3) No stickiness at the time of stinging It is an evaluation method by sensory test, dividing hair into left and right,
3.0 g of the sample and 3.0 g of the control shampoo (commercially available shampoo) were put on each divided hair, shampooed, and stickiness of the hair after rinsing was evaluated.

Evaluation criteria ○: No stickiness compared to commercial shampoo △: 〃 slightly sticky ×: 〃 sticky foam feeling (foam viscosity) After dividing hair into 2 minutes and applying 3 g of the comparative sample and the test sample to each side, foam The feel of the foam is evaluated by 10 testers by sensory evaluation based on the following criteria. In addition, as a comparative sample, sodium polyoxyethylene alkyl ether sulfate abbreviated as AES-Na (average EO addition mol number = 3,
Alkyl group: C ₁₂ / C ₁₃ = 1/1) was used.

++: Clearly the feel of the foam is better than AES-Na.

+: The foam feels slightly better than AES-Na.

±: It has a foam feeling similar to that of AES-Na.

−: Inferior to AES-Na in foam feeling.

-: The foam feel is much inferior to that of AES-Na.

[Examples 1 to 5 and Comparative Examples 1 and 2] Examples 1 to 5 and Comparative Examples 1 and 2 having the compositions shown in Table 1.
Shampoo composition was prepared and its performance was evaluated according to the above method. The results are shown in Table 1. In addition, all the added amounts are wt% (the same applies to the following Examples and Comparative Examples).

In Table 1, anion activator * 1 and polyalkylene glycol * 2 are the following compounds, respectively.

* 1: C ₁₄ sodium α-olefin sulfonate R: tallow alcohol residue n: 60 MW ≈ 3000 [Examples 6 to 10 and Comparative Examples 3 to 4] Examples 6 to 10 and Comparative Examples 3 to 4 having the compositions shown in Table 2.
A shampoo composition was prepared and the performance was evaluated in the same manner as above. The results are shown in Table 2.

In Table 2, anion activators * 1 and polyalkylene glycols * 2 are the same as above, and amphoteric activators * 3 are the following compounds.

R: C12 alkyl group [Examples 11 to 13] The shampoo compositions of Examples 11 to 13 having the compositions shown in Table 3 were prepared, and the performance was evaluated in the same manner as above. The results are shown in Table 3.

In Table 3, anion activator * 1, polyalkylene glycol * 2, and amphoteric activator * 3 are the same as above.

[Examples 14 to 23, Comparative Examples 5 to 9] Examples 14 to 23 and Comparative Examples 5 to 9 having the compositions shown in Table 4.
A shampoo composition was prepared and the performance was evaluated in the same manner as above. The results are shown in Table 4.

In Table 4, the anion activators * 1, polyalkylene glycols * 2, and amphoteric activators * 3 are the same as those described above, and the anion activators * 4, * 5, *
6, * 7, polyalkylene glycol * 8, * 9 and amphoteric activator * 10 are the following compounds.

* 4: Sodium polyoxyethylene alkyl ether sulfate * 5: C ₁₄ Sodium paraffin sulfonate -C ₁₈ * 6: N-lauroyl glutamic acid triethanolamine * 7: N-lauroyl -N- glycine triethanolamine R: tallow alcohol residue n: 40 R: Beef tallow alcohol residue n: 80 [Examples 24 to 27] The shampoo compositions of Examples 24 to 27 having the compositions shown in Table 5 were prepared, and the performance was evaluated in the same manner as above. The results are shown in Table 5.

In Table 5, anion activator * 1 and amphoteric activator * 3 are the same as those described above, and polyalkylene glycol * 11, * 12, * 13, R: Hexyl alcohol residue n: 60 R: Hebenyl alcohol residue n: 60 R: Beef tallow alcohol residue n: 60 R: Beef tallow alcohol residue n: 60 From the results of Tables 1 to 5, when the anion activator is used in combination with 0.5 to 10% of the total composition of the polyalkylene glycol, the low temperature stability, foam viscosity and conditioning property of the anion activator are improved. Is recognized.

Example 28 A shampoo composition having the following composition was prepared and evaluated.

Alpha sodium olefin sulfonate (C ₁₄ ) 10
% By weight paraffin sodium sulfonate 3〃 polyoxide decylene (1) polyoxyethylene (60)
Beef tallow alkyl ether 3 〃 Coconut oil fatty acid diethanolamide 4 〃 Anhydrous sodium sulfate 1 〃 Perfume 0.5 〃 UV absorber 0.1 〃 Dye micro- purified water balance 100.0 〃 (-5 ℃) Low temperature stability …… ○ Static friction coefficient …… 1.7 Smoothness of hair …… ○ No stickiness during rinsing ○○ Feeling of foam ＋+ [Example 29] A shampoo composition having the following composition was prepared and evaluated.

N-lauroyl-N-ethylglycine triethanolamine 10% by weight sodium paraffin sulfonate 4〃 polyoxide decylene (1) polyoxyethylene (60)
Beef tallow alkyl ether 5 〃 Coconut oil fatty acid diethanolamide 3 〃 Amidoamine type amphoteric activator 3 〃 Anhydrous sodium sulfate 1 〃 Fragrance 0.5 〃 Ultraviolet absorber 0.1 〃 Dye micro- purified water balance 100.0〃 (-5 ℃) Low temperature stability… … ○ Coefficient of static friction …… 1.6 Smoothness of hair …… ◎ No stickiness during rinsing …… ○ Feeling of foam …… ＋＋＋

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Claims (2)

[Claims] 1. A shampoo composition containing an anion activator, comprising the following formula (1): (However, R ₁ is a fatty alcohol residue having 8 to 22 carbon atoms, and n is
40 to 80 mol, Y represents a linear or branched alkyl group having 8 to 22 carbon atoms. ) The polyalkylene glycol represented by
A shampoo composition comprising 0.5 to 10% by weight. 2. A shampoo composition according to claim 1, which comprises a polyalkylene glycol of the formula (1) and a nitrogen-containing amphoteric activator.