JP6085454B2 - Washing soap - Google Patents

Description

  The present invention relates to a cleaning agent for cleaning hair, scalp, skin and the like.

  In detergents such as facial cleanser and shampoo for washing hair, a plurality of surfactants selected from nonionic surfactants, amphoteric surfactants, anionic surfactants, and cationic surfactants should be blended Has become commonplace. In addition, raw materials suitable for the characteristics required by the user are further blended in the cleaning agent, and there are proposals for further improvement of the characteristics and blending of raw materials to meet the newly required characteristics.

  Patent Document 1 contains a cationic surfactant, a solid oil (such as higher alcohol), a clay mineral, and a nonionic polymer compound as a shampoo that has good foaming and can suppress a squeaky feeling during rinsing. There is a proposal of a shampoo in which a liquid crystal structure mainly composed of a surfactant and a solid oil is dispersed. As a specific example of this proposal, Patent Document 1 describes that containing 4 to 8% by mass of a higher alcohol which is a solid oil.

  In addition to Patent Document 1, there are many proposals for cleaning agents. Patent Document 2 has good foaming, can suppress squeaky feeling during rinsing, has excellent smoothness after drying, and suppresses hairiness. Further, as a shampoo having a stable liquid crystal structure, a shampoo containing a carboxylic acid surfactant, a cationic surfactant, a higher alcohol, and a water-swellable clay mineral, and not containing an amphoteric polymer or a cationic polymer There are suggestions. Specific examples thereof include those containing 5.5 to 7% by mass of higher alcohol, 1.0% by mass of anionic surfactant (N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine) and higher alcohol 2 Those containing 1% by mass are described.

  The raw material-blended cleaning agents as described in Patent Document 1 and Patent Document 2 are generally used after being discharged from a pump container. Even from this method of use, the cleaning agent is usually set to a viscosity and fluidity that can be easily discharged from the pump container.

JP 2004-307463 A JP 2005-187342 A

  By the way, in hair washing and face washing, a scalp or facial massage may be performed for a relaxing effect or the like. At this time, since the massage can be smoothly performed with the cleaning agent having a lubricating action, it is required to suppress the flow of the cleaning agent during the massage that requires a longer time than the cleaning only. In order to realize this suppression, the viscosity of the cleaning agent may be increased. However, simply increasing the viscosity results in a thixotropic cleaning agent that is not suitable for massage.

  In view of the above circumstances, an object of the present invention is to provide a cleaning agent that has a thixotropic property that is difficult to flow down after application and is suitable for massaging the scalp and the like.

  As a result of intensive studies by the present inventors, in a cleaning agent in which an anionic surfactant as a cleaning component is blended, a layered clay mineral, a higher alcohol, and a cationic surfactant are also blended, and the blending amount of these raw materials By appropriately adjusting, the storage elastic modulus and the loss elastic modulus at a specific angular frequency are in a predetermined relationship, and it has been found that a thixotropic detergent that can be easily massaged such as the scalp can be obtained. In addition, the detergent having a predetermined relationship between the storage elastic modulus and the loss elastic modulus was also found to be difficult to flow down after being applied. From the above findings, the present invention has been completed.

That is, the cleaning agent according to the present invention contains a layered clay mineral, a higher alcohol, a cationic surfactant, and an anionic surfactant, and has an angular frequency measured by a rheometer under the following measurement condition (I) of 90 rad / storage modulus at s is greater than the loss modulus, the viscosity ratio of a shear rate 90s ^-1 for viscosities at shear rate 18s ^-1 measured by the following measurement conditions (II) with a rheometer, 0 .50 or less.
<Measurement conditions (I)>
Sensor: Cone plate sensor with a diameter of 35 mm and an inclination angle of 2 ° Stress: 2.0 Pa
Temperature: 25 ° C
<Measurement conditions (II)>
Sensor: Cone plate with a diameter of 35 mm and an inclination angle of 2 ° Sensor temperature: 25 ° C

  The storage elastic modulus is preferably larger than the loss elastic modulus at the angular frequency of 80 rad / s. If it is such a storage elastic modulus, it will be excellent in suppression of the flow-off of the washing | cleaning agent after application | coating.

  The ratio of the viscosity is preferably 0.45 or less. Such a viscosity ratio provides a thixotropic cleaning agent suitable for massage.

  The cleaning agent according to the present invention may be used as a shampoo for cleaning hair. By using it as a shampoo, you can massage the scalp at the same time.

  The blending amount of the layered clay mineral in the cleaning agent according to the present invention is preferably 0.1% by mass or more. Moreover, the compounding quantity of the said higher alcohol in the cleaning agent which concerns on this invention is good in it being 1.0 mass% or less. If the amount of the layered clay mineral and / or higher alcohol is such an amount, it is suitable for setting the ratio of the storage elastic modulus to the viscosity within the above range.

In order to increase the viscosity of the cleaning agent according to the present invention, for example, a fatty acid amide represented by the following general formula (I) may be blended.
[In the above general formula (I), R ¹ —CO represents a fatty acid residue having 12 to 24 carbon atoms, R ² represents an alkanol group having 2 to 4 carbon atoms, and R ³ represents 2 to 4 carbon atoms. The following alkanol groups or alkyl groups having 1 to 3 carbon atoms are represented. ]

  The cleaning agent according to the present invention contains a laminar clay mineral, a higher alcohol, and a cationic surfactant together with an anionic surfactant, and has a predetermined relationship between storage elastic modulus and loss elastic modulus at a specific angular frequency, and thixotropic properties. Therefore, it is difficult to flow down after application, and it is easy to massage skin such as the scalp.

It is a graph of storage elastic modulus (G ') and loss elastic modulus (G' ') of each example. It is a graph of the storage elastic modulus (G ') and loss elastic modulus (G' ') of a comparative example.

Based on an embodiment of the present invention, the present invention will be described below.
The cleaning agent according to the present embodiment has a predetermined elastic modulus and a predetermined thixotropic property. This detergent is a layered clay mineral, a higher alcohol, a cationic surfactant, and an anionic surfactant blended with water (the blending amount of water is, for example, 60% by mass or more), and if necessary, Known raw materials for cleaning agents are blended as optional raw materials.

(Storage modulus)
The cleaning agent of this embodiment has the following characteristics. That is, using a rheometer, the storage elastic modulus of the cleaning agent of the present embodiment (hereinafter, “storage elastic modulus” may be referred to as “G ′”) and loss elastic modulus (hereinafter “ “Loss elastic modulus” may be referred to as “G ″”.) G ′ and G ″ may be taken as the vertical axis, and angular frequency (hereinafter, “angular frequency” may be referred to as “ω”). In the graph having the horizontal axis of “Yes”, the G ′ line and the G ″ line intersect when ω is 90 rad / s or less.
<Rheometer measurement conditions>
Sensor: Cone plate sensor with a diameter of 35 mm and an inclination angle of 2 ° Stress: 2.0 Pa
Temperature: 25 ° C

  The cleaning agent of the present embodiment is one in which G ′ is larger than G ″ when ω is 90 rad / s, and G ′ is larger than G ″ when ω is 80 rad / s. good. With such a relationship between G ′ and G ″, it is possible to reduce the flow of the cleaning agent after it is applied to the object to be cleaned.

(Thixotropic properties)
The viscosity measured under the following measurement condition (II) using the cleaning agent rheometer of the present embodiment increases as the shear rate (hereinafter, “shear rate” is sometimes referred to as “dγ / dt”) increases. , Low value.
<Measurement conditions (II)>
Sensor: Cone plate with a diameter of 35 mm and an inclination angle of 2 ° Sensor temperature: 25 ° C

Cleaning agent of the present embodiment, the ratio of the viscosity at a shear rate of ^{90s -1} for viscosities at a shear rate of ^{18s -1} (eta ratio) are those becomes 0.50 or less, eta ratio is 0.45 or less It is good and 0.30 or less is preferable. If it is in this η ratio range, it becomes a cleaning agent having thixotropy that extends when a force necessary for massage is applied, so that it is easy to massage skin such as the scalp. In addition, although the minimum of (eta) ratio is not specifically limited, For example, it is 0.15.

The viscosity of the cleaning agent of the present embodiment is preferably 5 Pa · s or more and 10 Pa · s or less, for example, on the condition that dγ / dt is 36 s ⁻¹ .

(Layered clay mineral)
The layered clay mineral blended in the cleaning agent of this embodiment has a property of taking up water molecules. The layered clay mineral removes dirt and waste on the skin.

  In the cleaning agent of the present embodiment, one or more selected from known layered clay minerals such as kaolin, smectite, and bentonite may be blended. As a compounding quantity in the layered clay mineral of this embodiment, it is good that they are 0.1 mass% or more and 2.0 mass% or less, and 0.3 mass% or more and 1.0 mass% or less are preferable. By making it 0.1% by mass or more, it is suitable for setting the G ′ and η ratio for suppressing flow-off after application and ease of massage, and by making it 2.0% by mass or less, it is layered Suitable for suppression of clay mineral precipitation.

(Higher alcohol)
If a higher alcohol is added to the cleaning agent of the present embodiment, the hair feel can be improved.

  When a higher alcohol is blended in the cleaning agent of this embodiment, examples of the higher alcohol include linear saturated alcohols such as cetyl alcohol, stearyl alcohol, aralkyl alcohol, and behenyl alcohol; linear unsaturated alcohols such as oleyl alcohol. Alcohol; branched saturated alcohols such as hexyl decanol, octyldodecanol, isocetyl alcohol, and isostearyl alcohol;

  One or two or more selected from higher alcohols may be added to the cleaning agent of this embodiment. 1.0 mass% or less is good, the compounding quantity of the higher alcohol in the cleaning agent of this embodiment is 0.8 mass% or less, and 0.5 mass% or less is more preferable. If it is 1.0 mass% or less, it is suitable for setting of G ′ and η ratio for facilitating the flow-down suppression after application and massaging, and if it exceeds 1.0 mass%, ω is 90 rad / s. In this case, it becomes difficult to set G ′ larger than G ″. The lower limit of the higher alcohol content is, for example, 0.1% by mass.

(Cationic surfactant)
If a cationic surfactant is blended in the cleaning agent of this embodiment, liquid crystal is formed with a higher alcohol, and a creamy touch is imparted. In addition, the blending can improve the feel of hair.

  When a cationic surfactant is added to the cleaning agent of the present embodiment, the cationic surfactant includes di-long-chain alkyldimethylammonium salts such as distearyldimethylammonium chloride, dicetyldimethylammonium chloride, and dicocoyldimethylammonium chloride. Mono long-chain alkyltrimethylammonium salts such as behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, cetyltrimethylammonium bromide; long-chain alkoxyalkyltrimethylammonium salts such as stearoxypropyltrimethylammonium chloride; It is done. The term “long-chain alkyl” as used herein means a linear or branched alkyl group having 8 or more carbon atoms, and when the carbon number is 16 or more and 22 or less, irritation to the skin is suppressed. From the viewpoint of the feel imparted to hair and hair.

  One or more selected from cationic surfactants may be added to the cleaning agent of the present embodiment. The blending amount of the cationic surfactant in the cleaning agent of the present embodiment is preferably an amount that can ensure the cleaning function by being significantly less than that of the anionic surfactant, and is, for example, 0.5% by mass or less. The lower limit of the amount is, for example, 0.1% by mass.

(Anionic surfactant)
A well-known anionic surfactant is good to mix | blend with the cleaning agent of this embodiment as a cleaning component.

  Examples of the anionic surfactant include sulfuric anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl aryl ether sulfates, fatty acid alkanolamide sulfates, fatty acid monoglyceride sulfates; alkane sulfonates, α -Olefin sulfonate, α-sulfo fatty acid methyl ester salt, acyl isethionate, alkyl glycidyl ether sulfonate, alkyl sulfosuccinate, alkyl sulfoacetate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, N-acyl methyl Sulfonic acid anionic surfactants such as taurine salts; carboxylic acid anionic surfactants such as alkyl ether carboxylates, fatty acid amide ether carboxylates, fatty acid amide ether carboxylic acids, acyl lactates; Is mentioned.

  One or two or more types of anionic surfactants may be added to the cleaning agent of this embodiment. The blending amount of the anionic surfactant in the cleaning agent of the present embodiment is not particularly limited, but is preferably 5% by mass or more and 15% by mass or less, and 8% by mass or more in order to exert sufficient detergency. 15 mass% or less is preferable.

(Optional raw material)
The optional raw material blended in the cleaning agent of the present embodiment is appropriately selected from known cleaning agent raw materials as raw materials for shampoos and the like. The raw materials are nonionic surfactants, amphoteric surfactants, polyhydric alcohols, sugars, ester oils, fats and oils, polymer compounds, amino acids, animal and plant extracts, microorganism-derived substances, inorganic compounds, fragrances, preservatives, sequestering metal ions. Agents, ultraviolet absorbers and the like.

In order to increase the viscosity of the cleaning agent of this embodiment, for example, a fatty acid amide represented by the following formula (I) may be blended.
[In the above general formula (I), R ¹ —CO represents a fatty acid residue having 12 to 24 carbon atoms, R ² represents an alkanol group having 2 to 4 carbon atoms, and R ³ represents 2 to 4 carbon atoms. The following alkanol groups or alkyl groups having 1 to 3 carbon atoms are represented. ]

R ¹ —CO in the above general formula (I) is a fatty acid residue such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, coconut oil fatty acid, isostearic acid, isopalmitic acid, etc. Is mentioned. Examples of R ² in the general formula (I) include a hydroxyethyl group, a hydroxypropyl group, and a hydroxyisopropyl group. Examples of R ³ include a hydroxyethyl group, a hydroxypropyl group, a hydroxyisopropyl group, and a methyl group. Group and ethyl group.

  Examples of the fatty acid amide represented by the general formula (I) include lauric acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamide, lauric acid N-methylethanolamide, myristic acid N- Examples include methylethanolamide, stearic acid N-methylethanolamide, and coconut oil fatty acid N-methylethanolamide.

  One or more selected from the fatty acid amides may be blended in the cleaning agent of the present embodiment. The compounding quantity of the said fatty acid amide in the cleaning agent of this embodiment is 1 mass% or more and 5 mass% or less, for example.

(PH)
The pH of the cleaning agent of the present embodiment may be a general cleaning agent pH, for example, 5.0 or more and 7.0 or less.

(Production method)
The method for producing the cleaning agent of the present embodiment includes, for example, a method of blending and stirring the layered clay mineral after blending materials other than the layered clay mineral and sufficiently dispersing the raw materials by stirring while heating.

(Use)
The cleaning agent of this embodiment is used for applications involving skin cleaning. Such uses include shampoos and facial cleansers for washing hair. Since it is a cleaning agent having thixotropic properties, it may be filled in a tube container.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

  Water, Moroccan lava clay, higher alcohol, behenyltrimethylammonium chloride, polyoxyethylene lauryl ether sodium sulfate (2EO), polyoxyethylene sulfosuccinate lauryl disodium, coconut oil fatty acid ethyl ester sodium sulfonate, coconut oil fatty acid N-methylethanolamide, lauryl glycol hydroxypropyl ether, coconut oil fatty acid amide propyl betaine, isostearamid propyl betaine, polyquaternium-10, polyquaternium-52, xanthan gum, ethylene glycol distearate, shea fat, polyethylene glycol 1540, dipropylene glycol , Glycerin, isopropanol, sodium chloride, citric acid, and ingredients selected from perfumes, the following examples The cleaning agent was produced.

The storage elastic modulus (G ′), the loss elastic modulus (G ″), and the viscosity (η) were measured for the manufactured detergents of Examples using a rheometer “Rheo Stress 6000” manufactured by HAAKE. G ′ and G ″ are measured in a frequency dependent mode under conditions of an angular frequency (ω) of 92 rad / s or less, a cone plate sensor (diameter 35 mm, tilt angle 2 °), stress 2.0 Pa, and temperature 25 ° C. went. η was measured in a steady flow curve mode under conditions of a shear rate (dγ / dt) of 18 to 90 s ⁻¹ , a cone plate sensor (diameter 35 mm, tilt angle 2 °), and a temperature of 25 ° C.

Moreover, about the cleaning agent of an Example, sensory evaluation of the ease of performing scalp massage (ease of performing massage) was performed as follows. The cleaning agent was applied so as to reach the entire scalp and scalp after washing with warm water, and the entire scalp was thoroughly massaged. Five evaluators evaluated the ease of massage at this time, based on the use of the cleaning agent of Example 3. The evaluation results are as follows.
(Double-circle): All five evaluators evaluated that it was easier to massage than a reference | standard (Examples 1 and 4).
(Circle): Three evaluators evaluated that it was easier to massage than a reference | standard (Example 2).

  Table 1 below shows the raw materials and amounts blended with water for the production of the cleaning agents of the examples, and the measurement results of G ′, G ″, and η. In addition, Table 1 also shows the evaluation results regarding ease of performing massage. FIG. 1 shows a graph based on the measured values of G ′ and G ″ in each example.

In Table 1, the following (1) to (3) can be confirmed. It has been confirmed that blending layered clay minerals, higher alcohols, and cationic surfactants improves flow suppression and thixotropy and facilitates massage.
(1) It was easy to perform a massage as the η ratio was lower than 0.50 (thixotropic properties increased).
(2) From the viewpoint of the difference between G ′ and G ″ at ω = 90 rad / s, if the amount of higher alcohol is increased, G ′ at ω = 90 rad / s may be smaller than G ″. To produce (contrast of Examples 1 and 2).
(3) The possibility of the above (2) increases when blending coconut oil fatty acid N-methylethanolamide, which is a fatty acid amide, to increase the viscosity (contrast of Examples 2 and 4).

  Further, from the diagram of G ′ and G ″ in FIG. 1, G ′ of the cleaning agents of Examples 1 to 4 was larger than G ″ at ω = 90 rad / s. It can be easily predicted that G ′ of the cleaning agents of 2 and 4 was larger than G ″ at ω = 80 rad / s.

  Comparative cleaning agents were water, sodium polyoxyethylene lauryl ether sulfate (2EO), sodium tetradecenesulfonate, sodium polyoxyethylene lauryl ether acetate (6EO), N-lauroyl-L- Sodium aspartate, sodium coconut oil fatty acid ethyl ester sulfonate, coconut oil fatty acid N-methylethanolamide, pyroglutamic acid isostearic acid polyoxyethylene hydrogenated castor oil (40 EO), polyoxyethylene lauryl ether (16 EO) And coconut oil fatty acid amidopropyl betaine, isostearic acid amidopropyl betaine, polyquaternium-10, polyquaternium-52, dipropylene glycol, glycerin, sodium chloride, preservatives, and fragrances.

  G ′ and G ″ of the cleaning agent of the comparative example were measured in the same manner as the cleaning agent of the above example. Table 2 below shows the raw materials and amounts blended with water for the production of the cleaning agent of the comparative example, and the measurement results of G ′ and G ″. FIG. 2 shows a graph based on the measured values of G ′ and G ″ of the comparative example.

  From Table 2 and FIG. 2, the cleaning agent of the comparative example in which the layered clay mineral, the higher alcohol, and the cationic surfactant were not blended had a relationship of G ′ <G ″ indicating fluidity at ω = 90 rad / s or less. Can be confirmed.

Claims (7)

Layered clay mineral, higher alcohol, cationic surfactant, and anionic surfactant are blended,
The amount of the layered clay mineral is 0.1 mass% or more,
The amount of the higher alcohol is 1.0% by mass or less,
The amount of the cationic surfactant is 0.5% by mass or less,
The amount of the anionic surfactant is 5% by mass or more and 15% by mass or less,
The storage elastic modulus at an angular frequency of 90 rad / s measured under the following measurement conditions (I) using a rheometer is larger than the loss elastic modulus,
Detergent ratio of viscosity at a shear rate of 90s ^-1 for viscosities at shear rate 18s ^-1 measured, characterized in that 0.50 or less in the following measurement conditions (II) with a rheometer.
<Measurement conditions (I)>
Sensor: Cone plate sensor with a diameter of 35 mm and an inclination angle of 2 ° Stress: 2.0 Pa
Temperature: 25 ° C
<Measurement conditions (II)>
Sensor: Cone plate with a diameter of 35 mm and an inclination angle of 2 ° Sensor temperature: 25 ° C   The cleaning agent according to claim 1, wherein the storage elastic modulus is larger than the loss elastic modulus at the angular frequency of 80 rad / s.   The cleaning agent according to claim 1 or 2, wherein the viscosity ratio is 0.45 or less.   The cleaning agent according to any one of claims 1 to 3, which is used as a shampoo for cleaning hair. The cleaning agent according to any one of claims 1 to 4, wherein polyquaternium-10 is blended . The cleaning agent according to any one of claims 1 to 5, wherein a blending amount of the higher alcohol is 0.5 mass% or less. The cleaning agent according to any one of claims 1 to 6, wherein a fatty acid amide represented by the following general formula (I) is blended.
[In the general formula (I), R ¹ —CO represents a fatty acid residue having 12 to 24 carbon atoms, R ² represents an alkanol group having 2 to 4 carbon atoms, and R ³ represents 2 to 4 carbon atoms. The following alkanol groups or alkyl groups having 1 to 3 carbon atoms are represented. ]