JPH0759715B2 - Hypoallergenic detergent composition - Google Patents

Abstract

A low irritant detergent composition composed of (A) an alpha -olefinsulfonic acid salt, (B) a surfactant of the sulfosuccinic acid ester type, (C) an amphoteric imidazole surfactant and (D) a nonionic alkanolamide surfactant is provided. The surfactant (B) is represented by the following formula: <CHEM> wherein R means R1O- @-CH2CH2O@m, R1 being a linear or branched alkyl or alkenyl group having 8-22 carbon atoms and m standing for a number of 1-20 on average, and M denotes a hydrogen atom or a cationic ion capable of forming a water-soluble salt selected from the group consisting of alkali metal ions, ammonium ion and organoammonium ions. The weight ratio of (A)/(B) is 1/3-3/1, that of (C)/(A) is 1/10-1/1, that of (D)/(A)+(B) is 1/20-1/2, and the sum of (A)+(B)+(C)+(D) accounts for 10-40 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a hypoallergenic detergent composition, more specifically, it has low irritation to skin and eyes and has good detergency and foaming power. Detergent composition.

[Conventional technology and its problems]

Naturally, the cleaning agent is required to have excellent detergency such as detergency and foaming power, as well as a cleaning agent for the human body (shampoo, body shampoo, etc.), detergent for dish utensils, light wool cleaning If the skin is in direct contact with cleaning agents such as agents,
In particular, it is required to have low irritation to the skin and eyes, and also to have a stable solution.

Surfactants, which are the main components of these detergents, are mainly linear alkylbenzene sulfonate (LAS), alkyl sulfate ester salt (AS), polyoxyethylene alkyl ether sulfate ester salt (AES), α-olefin sulfone salt. Anionic surfactants such as acid salts (AOS) have been used. However, although the anionic surfactants have good detergency, they are not the best main component surfactants for the detergents, since they both irritate the skin and eyes.

By the way, as a system which satisfies these requirements to some extent, it has recently been preferred to use polyoxyethylene alkyl ether sulfate in combination with an imidazoline-based amphoteric surfactant, especially in shampoo. However, in this combination, when the ratio of the polyoxyalkyl ether sulfate is high, the foaming property, detergency and other properties as a shampoo are satisfied, but the irritation is relatively high, while the imidazoline-based amphoteric surfactant is used. When the ratio is high, the irritation is low, but the foaming property and the detergency are insufficient.

In order to solve the above problems, in JP-A-62-127396, a sulfosuccinic acid type surfactant is blended as a third essential component. However, the sulfosuccinic acid-based surfactant is an anion surfactant having relatively low stimulative property by itself, and as shown in JP-A-56-38395, the sulfosuccinic acid-based surfactant can improve the stimulability of AES by combination with AES. Although it has a reducing effect, it is currently used only as a co-activator for AES because it generally lacks foaming power and low temperature stability.

On the other hand, in recent years, especially in Europe, attention has been paid to the by-product of dioxane in AES, and dedioxane is removed from AES.
Therefore, the development of a mild detergent containing no AES is desired.

As a cleaning agent characterized by not containing AES at all,
As a relatively similar one, there is a mixture of two components of a sulfosuccinic acid type surfactant and an imidazoline type amphoteric surfactant disclosed in JP-A-55-86892, but this also has a problem in foamability.

[Means for solving problems]

The present inventor has conducted extensive studies to solve the above problems, and as a result, (A) α-olefin sulfonate, (B) a specific sulfosuccinate ester-based surfactant, (C) an imidazoline-based amphoteric surfactant, and ( D) By adding an alkanolamide type nonionic surfactant, it is possible to obtain a detergent composition which can reduce irritation without impairing foaming power and detergency, and can also satisfy solution stability. Found,
The present invention has been completed.

That is, the present invention includes (A) α-olefin sulfonate, (B) the following formula [I] [In the formula, R represents R ₁ OCH ₂ CH ₂ O _m (R ₁ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and m represents a number of 1 to 20 on average). And M represents hydrogen, or a cation forming a water-soluble salt selected from the group consisting of alkali metals, ammonium and organic ammonium], and a sulfosuccinate-based surfactant represented by
The (C) imidazoline-based amphoteric activator and (D) alkanolamide type nonionic activator have a (A) / (B) weight ratio of 1/3 to 3/1 and a (C) / (A) weight ratio of 1/10 to 1/1,
The weight ratio of (D) / (A) + (B) becomes 1/20 to 1/2,
Furthermore, the total weight of (A) + (B) + (C) + (D) is 10-40.
It is intended to provide a hypoallergenic detergent composition, which is characterized in that it is contained in a weight percentage.

Examples of the (A) α-olefin sulfonate used in the present invention include the following formula [V] R ₁₀ —SO ₃ M ″ [V] [wherein R ₁₀ is a straight chain having an average carbon number of 8 to 22 or A branched alkenyl group or an alkyl group substituted by a hydroxyl group, M ″ represents hydrogen or a cation forming a water-soluble salt selected from the group consisting of alkali metals] and a sulfated product of α-olefin represented by the formula: To be
The average carbon number of R ₁₀ is particularly preferably 14 to 16 from the viewpoint of foamability and stability of the composition.

As the sulfosuccinate ester-based surfactant (B) in the present invention, those having an ethoxy group derived from the higher alcohol ethoxylate represented by the formula [I] or the higher fatty acid amide are used. As the polymerization number m of the ethoxy group in the formula [I] increases, the irritation decreases, but the basic performance as a cleaning agent decreases. Therefore, it is more preferably 2 to 10. As the higher alcohol represented by R ₁ OH, not only primary alcohols but also secondary alcohols are preferably used.

Examples of the (C) imidazoline-based amphoteric surfactant in the present invention include the following compounds (amidoamine-type amphoteric surfactant, etc.) and the like.

Formula [II] [Wherein R ₂ is a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, and R ₃ is —CH ₂ COOM ′ or —CH ₂ CH ₂ COOM ′ (M ′ is the same as above). R ₄ is hydrogen, −
CH ₂ COOM 'or -CH ₂ CH ₂ COOM' (M 'is the same as above)
] The tertiary amide type imidazoline-based amphoteric surfactant represented by

Formula [III] [In the formula, R ₅ is hydrogen, -CH ₂ COOM 'or -CH ₂ CH ₂ COOM'
(M 'is the same as the above), and R ₂ and R ₄ are the same as the above].] A secondary amide type imidazoline-based amphoteric surfactant.

Formula (IV) [In the formula, R ₆ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ₇ represents hydrogen or -C ₂ H ₄ OH.
The, R ₈ is _{-C 2 H 4 OH, -C 2} H 4 OC 2 H 4 COOM ' , or -C ₂ H ₄ COO
M '(M' is the same as above), R ₉ is hydrogen or -C ₂ H ₄ COO
M '(M' is the same as above)] and an α-position-added imidazoline-based amphoteric surfactant.

These compounds are used alone or in combination of two or more. Further, as the R ₂ CO-group in the above formula [II] or the R ₆ CHCO-group in [IV], those derived from lauric acid, oleic acid, coconut oil fatty acid and palm kernel oil fatty acid are preferable. M'is sodium, hydrogen,
Most preferred is the triethanolamine salt.

Examples of the (D) alkanolamide type nonionic activator in the present invention include compounds represented by the following formula [VI] [In the formula, R ₁₁ is a linear or branched alkyl group or alkenyl group having an average carbon number of 7 to ₂₁ , R ₁₂ and R ₁₃ are hydrogen, 2-
Which represents a hydroxyethyl group or a 2-hydroxypropyl group].

In the present invention, the weight ratio of (A) / (B) is 1/3 to 3/1. If (A) / (B) exceeds 3/1, a sufficiently hypoallergenic composition cannot be obtained, and in order to make it hypoallergenic, a large amount of component (C) must be blended and the detergency Also, it is not preferable because foaming trouble occurs. (A) /
If (B) is smaller than 1/3, a composition that is sufficiently stable at low temperature cannot be obtained, which is not preferable.

The weight ratio of (C) / (A) is 1/10 to 1/1. When (C) / (A) is less than 1/10, detergency and foaming power are sufficient, but a mild composition cannot be obtained. Conversely, when it exceeds 1/1, foaming power and stability are stable. It is not preferable because it causes sexual disorders.

The weight ratio of (D) / (A) + (B) is 1/20 to 1/2. If it exceeds 1/2, foam breakage becomes poor, and if it becomes less than 1/20, foaming of the cleaning agent decreases and the state of foam also deteriorates, which is not preferable.

In the composition of the present invention, (A) + (B) + (C) +
It is used so that the total weight of (D) is 10 to 40% by weight in the entire composition. If it is less than 10% by weight, sufficient foaming power cannot be obtained,
If it exceeds 40% by weight, a uniform and stable composition cannot be obtained, which is not preferable.

The cleaning composition of the present invention includes these (A), (B),
In addition to the essential components (C) and (D), surfactants generally used in detergents can be used in a total amount of 0 to 10% by weight. Also, dissolution aids such as glycerin, propylene glycol, ethanol, urea; water-soluble polymers,
A polyethylene glycol fatty acid ester, a thickener such as salt, a preservative such as paraben, and an antioxidant such as BHT can be used in a total amount of 0 to 20% by weight for shaping and stabilizing. Furthermore, pigments, fragrances, anti-dandruff agents, anti-inflammatory agents, vitamins, plant extracts, proteins and their derivatives or decomposition products can be used in a total amount of 0 to 5% by weight. The balance is water, which ranges from 30 to 90% by weight.

The detergent composition of the present invention can be made into various dosage forms such as liquid (rosion), paste and gel if desired. pH should be 4 to 1 using acid or alkali if necessary.
It is adjusted to 0, more preferably 5.5 to 7.5.

[Operation and effect of the invention]

According to the present invention, it is possible to obtain a detergent that is hypoallergenic and has excellent detergency. Therefore, the composition of the present invention can be used as, for example, hair for infants, skin cleanser, kitchen detergent for housewives with rough hands, daily shampoo for those who wash their hair daily, and professionally for a long time. It is suitable as a hypoallergenic hairdressing shampoo for people who have no choice but to contact.

〔Example〕

Next, examples will be described. Each test in Examples was carried out by the following method.

(1) Foaming power test method 0.5% of artificial dirt was added to a 1% aqueous solution of a detergent composition, and a flat propeller was rotated in the cylinder at 40 rpm for 10 minutes at a rotation speed of 1000 rpm for 5 minutes in a cylinder. Stirring was performed, and after the stirring was completed, evaluation was performed by the amount of foam 30 seconds later.

Sensory evaluation using a fluff After adding warm water (40 ° C.) to a 25 g fluff, 0.5 g of the detergent composition was applied and squeezed for about 2 minutes, and the amount of foam was sensory evaluated.

Evaluation criteria ◎ Well foamed ○ Normal △ Somewhat poorly foamed × Poorly foamed (2) Detergency test method Artificial contaminated cloth An artificial oily dirt is uniformly dispersed in a solvent, and a wool muslin wool cloth is brought into contact with this solution and dried. Then, artificial oily dirt is attached uniformly. This cloth was used as an experiment by making a 10 cm × 10 cm test piece.

Washing condition and washing method A detergent composition is dissolved in German hardness 15 ° d hard water to prepare a 3% detergent composition aqueous solution 1. Five artificially contaminated cloths and this aqueous solution are transferred as they are to a stainless beaker for a tergotometer, and agitated with a tergotometer at 75 rpm, 40 ° C. for 3 minutes. After rinsing under running water, it was ironed and pressed for reflectance measurement.

Evaluation of Detergency Each detergent composition was evaluated by comparing it with the detergency of a standard detergent having the following composition.

○ Equivalent or better than the standard product × Inferior to the standard product Standard detergent composition Alkyl sulfate ester salt (SAPANOL VS from KAO Corp. SA) 15.0% Alkanolamide (Amidet B-112 from KAO Corp. SA) 3.0% Water balance (3) Ocular mucosal irritation test method The primary irritation test of the ocular mucosa is the French standard method (Jounal
Official Rpub Francaise24-Oct-84). Briefly, 6 rabbits are used and the right eye is contacted with 0.1 ml of sample stock solution. After that, washing is not performed, and observation is performed 24 hours, 48 hours, and 72 hours later. At that time, for observation, contact with sodium fluorecein and washing with physiological saline. The left eye is standard.

Since the evaluation obtains a quantitative value, the Code of Federal Requla
This was done in accordance with tions of the USA, Title16 Section 1500.42. The outline of the Edema state of the conjunctiva (A)
4 stages, Redness state (C) in 3 stages, Iris state (D) in 2 stages, Corneal cloudiness state (E) in 4 stages, and eye mucosal irritation index EI I To calculate.

EI I = (A + C) × 2 + D × 5 + E × 5 Therefore, the maximum stimulation index is 44.

(4) Stability test Store at 5 ° C, room temperature, 40 ° C and 50 ° C for 1 month, and evaluate appearance, pH, viscosity and grading every week.

Examples 1 to 6 and Comparative Examples a to c Liquid detergent compositions having the compositions shown in Table 1 were prepared, and their foaming power, detergency, stability and eye mucous membrane irritation were evaluated. The pH of each composition was adjusted to 7.0 with a small amount of citric acid.

Examples 7 to 9 and Comparative Examples d to e Liquid detergent compositions having the compositions shown in Table 2 were prepared and evaluated for foaming power, stability, eye mucous membrane irritation and dioxane concentration in the system.

Example 10 Pearly shampoo wt% α-Olefin sulfonic acid (AOS ¹⁾ ) 10.0 Sulfosuccinate (NES ² ) 8.0 Imidazoline-type activator (SC-23 ⁾ ) 2.0 Alkanolamide (A-11 ⁹⁾ ) 3.0 Ethylene glycol distearate 1.0 Fragrance, colorant, slight amount of water balance When a shampoo was prepared according to the above formulation, the appearance, feeling of use, foaming and detergency were good. ¹⁾ , ²⁾ , ³⁾ : Same as above ⁹⁾ A-111: Amidet A-111 manufactured by KAO CORPORATION SA (monoethanol coconut amide manufactured from refined coconut oil and monoethanolamine) Example 11 Conditioning Shampoo Weight% α-Olefin Sulfonic Acid (AOS ¹⁾ ) 10.0 Sulfosuccinate (NES ² ) 5.0 5.0 Imidazoline Activator (SC-2 ³ ) 5.0 Alkanolamide (B-1 12 ⁴⁾ ) 3.0 Cationic Polymer Morquat 550 (Merck) 0.05 Sodium chloride 0.5 Fragrance, Dye Microscopic water balance ¹⁾ , ²⁾ , ³⁾ , ⁴⁾ : The same as above, but when the conditioning shampoo was prepared, the washing and foaming properties were obtained. It had a good feeling of use, and had an excellent feeling as a moisturizing hair after washing.

Example 12 Conditioning shampoo wt% α-Olefin sulfonic acid (AOS ¹⁾ ) 8.0 Sulfosuccinic acid ester (NES ² ) 8.0 8.0 Imidazoline-type activator (SC-2 ³ ) 4.0 Alkanolamide (B-1 12 ⁴⁾ ) 3.0 Cationized cellulosic polymer JR-400 (manufactured by UCC) 0.20 Fragrance, colorant Microscopic water balance ¹⁾ , ²⁾ , ³⁾ , ⁴⁾ : The same formulation as above was used to prepare the conditioning shampoo. It had good detergency and foamability and was good as a moisturizer for washing hair.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C11D 1:52 1:88) (56) References JP-A-55-86893 (JP, A) Special features Open Sho 58-7495 (JP, A)

Claims (2)

[Claims] 1. (A) α-Olfine sulfonate,
(B) The following formula [I] [In the formula, R represents R ₁ OCH ₂ CH ₂ O _m (R ₁ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and m represents a number of 1 to 20 on average). And M represents hydrogen, or a cation forming a water-soluble salt selected from the group consisting of alkali metals, ammonium and organic ammonium], and a sulfosuccinate-based surfactant represented by
The (C) imidazoline-based amphoteric activator and (D) alkanolamide type nonionic activator have a (A) / (B) weight ratio of 1/3 to 3/1 and a (C) / (A) weight ratio of 1/10 to 1/1,
The weight ratio of (D) / (A) + (B) becomes 1/20 to 1/2,
Furthermore, the total weight of (A) + (B) + (C) + (D) is 10-40.
A hypoallergenic detergent composition, characterized in that the detergent composition is contained in a weight percentage. 2. The hypoallergenic detergent according to claim 1, wherein the imidazoline-based amphoteric surfactant (C) is one or more selected from the group consisting of the following compounds. Composition. Formula [II] [Wherein R ₂ is a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, and R ₃ is —CH ₂ COOM ′ or —CH ₂ CH ₂ COOM ′ (M ′ is hydrogen or an alkali). metal,
Alkaline earth metals, are shown a cation) to form a water soluble salt selected from the group consisting of ammonium and organic ammonium, R ₄ is hydrogen, -CH ₂ COOM ', or -CH ₂ CH ₂ COO
M '(M' is the same as above)], and a tertiary amide type imidazoline-based amphoteric surfactant. Formula [III] [In the formula, R ₅ is hydrogen, -CH ₂ COOM 'or -CH ₂ CH ₂ COOM'
(M 'is the same as the above), and R ₂ and R ₄ are the same as the above].] A secondary amide type imidazoline-based amphoteric surfactant. Formula (IV) [In the formula, R ₆ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ₇ represents hydrogen or -C ₂ H ₄ OH.
The, R ₈ is _{-C 2 H 4 OH, -C 2} H 4 OC 2 H 4 COOM ' , or -C ₂ H ₄ COO
M '(M' is the same as above), R ₉ is hydrogen or -C ₂ H ₄ COO
M '(M' is the same as above)] and an α-position-added imidazoline-based amphoteric surfactant.