Hair cleansing composition

Abstract

The present invention relates to a hair cleaner composition which uses a specific internal olefin sulfonic acid or salt thereof, improves performance when applied to hair, and has excellent low-temperature stability. That is, the present invention relates to a hair cleaner composition which contains the following components (A) and (B): (A) an internal olefin sulfonic acid or salt thereof having 16 carbon atoms, which is obtained by sulfonating a raw material olefin having 16 carbon atoms and having an average double bond position of 3.9 or more and 4.5 or less, and (B) a cationic polymer, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) being 1 or more and 500 or less.

Description

Technical Field

[0001] This invention relates to a hair cleaning agent composition. Background Technology

[0002] Olefin sulfonates, known for their various carbon atom numbers, have been used to date in a variety of cleaning agent compositions due to their excellent performance as anionic surfactants.

[0003] For example, Patent Document 1 discloses a detergent composition containing an inner olefin sulfonate with 12 to 24 carbon atoms and a specific anionic surfactant that does not contain sulfuric acid groups. This composition attempts to provide good foam retention, quick rinsing, and good combing properties for hair while being able to contain various other surfactants. Patent Document 2 discloses a skin or hair detergent composition containing the same inner olefin sulfonate as described above and a cationic or amphoteric polymer. This composition attempts to improve foam retention and rinsing properties while being able to contain various other surfactants, and to provide a good feel such as combing properties and a moisturizing sensation when applied to hair or skin.

[0004] Furthermore, Patent Document 3 discloses a skin or hair cleanser composition containing a specific cationic cellulose ether and other cationic polymers, and which may contain an olefin sulfonate with 12 to 24 carbon atoms as an anionic surfactant, which improves combability or smoothness, durability and coverage when applied to hair or skin.

[0005] (Patent Document 1) Japanese Patent Application Publication No. 2015-27976

[0006] (Patent Document 2) Japanese Patent Application Publication No. 2015-27975

[0007] (Patent Document 3) Japanese Patent Application Publication No. 2014-131989 Summary of the Invention

[0008] The present invention provides a hair cleaning agent composition comprising the following components (A) and (B):

[0009] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0010] (B) Cationic polymers,

[0011] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0012] Furthermore, while olefin sulfonates can impart various excellent properties to the composition as described above, their hydrophobicity increases and melting point rises with increasing carbon chain length, making them prone to precipitation and leading to a decrease in the low-temperature stability of the composition. However, none of the aforementioned patent documents have explored aspects that contribute to good low-temperature stability, leaving room for improvement.

[0013] Therefore, the inventors conducted various studies and found that by sulfonating a specific internal olefin sulfonic acid or its salt, which is formed by sulfonating a raw material olefin with an average double bond position within a very limited range, and a cationic polymer in a specific mass ratio, a hair cleaning agent composition that exhibits excellent shampooing effect and good low-temperature stability can be obtained.

[0014] Specifically, the present invention relates to a hair cleaning agent composition that uses a specific olefin sulfonic acid or its salt, which improves its performance when applied to hair and has excellent low-temperature stability.

[0015] The hair cleaning composition according to the present invention provides good foaming properties and smooth foam when applied to hair, and the hair feels truly soft when rinsed. Moreover, the composition has excellent low-temperature stability and is a highly useful composition.

[0016] Furthermore, the term "good foaming properties" when washing hair using the hair-cleansing composition of the present invention refers to the ability to quickly generate foam during shampooing and the sufficient amount of foam required to effectively remove dirt. Additionally, the term "smooth foam texture" when washing hair using the hair-cleansing composition of the present invention refers to a smooth foam texture that is refreshing and soft, and provides a noticeable protective effect from the hair roots to the tips. Furthermore, the term "softness of hair" when rinsing after washing hair using the hair-cleansing composition of the present invention refers to the fact that not only does the hair feel soft and elastic overall during rinsing, but each hair also feels supple and healthy during styling.

[0017] Hereinafter, the effects of the hair cleaning composition of the present invention on hair, such as "good foaming properties", "smooth foam" and "softening of hair", will be collectively referred to as "shampooing effect". Detailed Implementation

[0018] The present invention will now be described in detail.

[0019] The hair-cleansing composition of the present invention contains a 16-carbon inner olefin sulfonic acid or its salt, obtained by sulfonating a raw material olefin with an average double bond position of 3.9 to 4.5 positions. That is, the 16-carbon inner olefin sulfonic acid or its salt of component (A) is a compound obtained by sulfonating a raw material olefin with an average double bond position within a specific and extremely limited range as a starting material; specifically, it is a compound obtained by neutralizing and hydrolyzing the sulfonated raw material olefin.

[0020] Salts of 16-carbon internal olefin sulfonates, obtained by sulfonating a 16-carbon olefin with an average double bond position of 3.9 to 4.5, can be selected from one or more of the following: alkali metal salts such as sodium and potassium salts; organic amine salts such as ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-aminoethanol salts, and 2-aminomethylpropanediol salts; and basic amino acid salts such as lysine salts and arginine salts. These 16-carbon internal olefin sulfonates do not need to be in salt form initially; salts generated through a neutralization reaction during the manufacturing process can also be used.

[0021] From the viewpoint of improving low-temperature stability, the salt of the internal olefin sulfonic acid with 16 carbon atoms is preferably selected from one or more of sodium salt, potassium salt, ammonium salt and 2-aminoethanol salt, more preferably selected from one or two of sodium salt and potassium salt, and even more preferably sodium salt, that is, sodium internal olefin sulfonate with 16 carbon atoms.

[0022] In addition, the product obtained from the 16-carbon olefin, i.e. component (A), is mainly a mixture of 16-carbon olefin sulfonic acid or its salt, which is a 16-carbon hydroxyalkane sulfonic acid or its salt (hydroxyl body, abbreviated as "HAS") and 16-carbon olefin sulfonic acid or its salt (olefin body, abbreviated as "IOS").

[0023] Furthermore, regarding the 16-carbon olefin as the starting material for component (A), it is primarily an olefin with the double bond located inside the carbon chain, but sometimes also contains trace amounts of so-called α-olefins with the double bond located at position 1 of the carbon chain. When this starting olefin is sulfonated, β-sulfonolactone is mainly generated, and a portion of the β-sulfonolactone is converted into γ-sulfonolactone and olefin sulfonic acid. Further, these β-sulfonolactones, γ-sulfonolactones, and olefin sulfonic acids are converted into 16-carbon hydroxyalkane sulfonic acids or their salts and 16-carbon olefin sulfonic acids or their salts in a neutralization-hydrolysis step (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). In addition, the hydroxyl group of the obtained hydroxyalkane sulfonic acid or its salt is located inside the alkane chain, and the double bond of the olefin sulfonic acid or its salt is located inside the olefin chain.

[0024] Therefore, in this specification, these products and mixtures thereof are collectively referred to as 16-carbon olefinic acids or their salts of component (A).

[0025] The average double bond position of the 16-carbon olefin sulfonic acid or its salt formed by sulfonation is between positions 3.9 and 4.5. For 16-carbon olefins with such average double bond positions, the double bond positions include the possible trace amount of position 1, and are widely distributed between positions 2 and 8.

[0026] In addition, the double bond positions and distribution of the starting olefin can be confirmed by gas chromatography-mass spectrometry (GC-MS). Specifically, by using a gas chromatograph (GC), components with different carbon chain lengths and double bond positions are accurately separated, and each component is placed in a mass spectrometer (MS). Thus, the double bond positions can be identified, and the double bond positions and distribution of the starting olefin can be determined from the peak areas of each GC.

[0027] On the other hand, regarding the 16-carbon olefin sulfonic acid or its salt obtained by sulfonating the starting olefin, the more internally located the sulfonic acid group introduced by sulfonation is in the carbon chain, the more difficult it is to separate; therefore, there is currently no definitive analytical method. However, the positions of the sulfonic acid groups in component (A) essentially correspond to the double bond positions of the starting olefin, so it can be reasonably inferred that they are located at positions 2 to 8, including position 1, without excessive bias, thus exhibiting a wide distribution. Therefore, in this invention, component (A) is defined based on the average double bond position value of the starting olefin.

[0028] The component (A) used in this invention is an inner olefin sulfonic acid or its salt obtained from a raw material olefin having the average double bond position value as described above, i.e., a wide double bond distribution, and the sulfonic acid group is present in a wide range of positions in the carbon chain without excessive bias. In an inner olefin sulfonic acid or its salt with 16 carbon atoms, if the sulfonic acid group is present in a position closer to the end of the carbon chain, it is easy to precipitate due to the increased melting point caused by the increased carbon chain length, and low-temperature stability may be compromised. In addition, if the sulfonic acid group is present in a position closer to the inside of the carbon chain, it may impair the foam texture during washing or the feel of the hair during rinsing, resulting in reduced shampooing effect. However, if the inner olefin sulfonic acid or its salt with 16 carbon atoms obtained from the above-mentioned raw material olefin is an inner olefin sulfonic acid or its salt with 16 carbon atoms, the sulfonic acid group is present in a wide range of positions in the carbon chain without excessive bias, thereby moderately mixing inner olefin sulfonic acids or their salts with various carbon chain lengths from the sulfonic acid group bonding position to the end. Therefore, it can maintain excellent shampooing effect and exhibit good low-temperature storage stability when combined with the following ingredient (B). The same applies when ingredient (A) is sodium sulfonate with 16 carbon atoms.

[0029] Furthermore, the average double bond position (in units of positions) of the 16-carbon-number olefins that are the starting materials of component (A) refers to the average double bond position of each 16-carbon-number olefin present in the total amount of the 16-carbon-number olefins. Specifically, the average double bond position of the 16-carbon-number olefins is a value obtained by the following equation (1).

[0030] Equation (1):

[0031]

[0032] In formula (1), n ​​is an integer representing the position of the double bond in the 16-carbon olefin (unit: position); Cn represents the content of the 16-carbon olefin with double bonds at position n in 100% mass of the total 16-carbon olefin (unit: mass%).

[0033] From the viewpoint of ensuring good low-temperature storage stability, the average double bond position of the 16-carbon olefin forming component (A) is at position 3.9 or higher, preferably at position 4.0 or higher, and more preferably at position 4.1 or higher. Furthermore, from the viewpoint of ensuring excellent shampooing effect, the average double bond position of the 16-carbon olefin is at position 4.5 or lower, preferably at position 4.4 or lower, and more preferably at position 4.2 or lower. Moreover, the average double bond position of the 16-carbon olefin is at position 3.9 or higher and position 4.5 or lower, preferably at positions 4.0 to 4.4, more preferably at positions 4.0 to 4.2, and even more preferably at positions 4.1 to 4.2.

[0034] Furthermore, the content of the olefin with the double bond position at position 2 in the 16-carbon olefin is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 35% by mass or less, more preferably 32% by mass or less, and even more preferably 24% by mass or less. The content of the olefin with the double bond position at position 2 in the 16-carbon olefin is preferably 10 to 35% by mass, more preferably 15 to 32% by mass, and even more preferably 20 to 24% by mass.

[0035] The content of the olefin with the double bond at position 3 in the 16-carbon olefin is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 30% by mass or less, more preferably 24% by mass or less, and even more preferably 19% by mass or less. Furthermore, the content of the olefin with the double bond at position 3 in the 16-carbon olefin is preferably 10 to 30% by mass, more preferably 14 to 24% by mass, and even more preferably 16 to 19% by mass.

[0036] The content of the olefin with the double bond position at position 4 in the 16-carbon olefin is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 17% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 19% by mass or less. Furthermore, the content of the olefin with the double bond position at position 4 in the 16-carbon olefin is preferably 10 to 30% by mass, more preferably 15 to 25% by mass, and even more preferably 17 to 19% by mass.

[0037] The content of the olefin with the double bond position at the 5-position in the 16-carbon olefin is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 13% by mass or more, and preferably 25% by mass or less, more preferably 19% by mass or less, and even more preferably 15% by mass or less. Furthermore, the content of the olefin with the double bond position at the 5-position in the 16-carbon olefin is preferably 5 to 25% by mass, more preferably 10 to 19% by mass, and even more preferably 13 to 15% by mass.

[0038] The content of the olefin with the double bond position at position 6 in the 16-carbon olefin is preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 11% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 13% by mass or less. Furthermore, the content of the olefin with the double bond position at position 6 in the 16-carbon olefin is preferably 5 to 20% by mass, more preferably 7 to 15% by mass, and even more preferably 11 to 13% by mass.

[0039] The total content of olefins with double bonds at positions 7 or 8 in a 16-carbon olefin is preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 12% by mass or more, and preferably 25% by mass or less, more preferably 22% by mass or less, and even more preferably 16% by mass or less. Furthermore, the total content of olefins with double bonds at positions 7 or 8 in a 16-carbon olefin is preferably 5 to 25% by mass, more preferably 7 to 22% by mass, and even more preferably 12 to 16% by mass.

[0040] The mass ratio of the content of 16-carbon olefins with double bonds at positions 3-5 to the content of olefins with double bonds at positions 6-8 (raw material olefins) 3～5 Position / raw material olefins 6～8 The content of the double bond position (position 1) is preferably 1.0 or more, more preferably 1.3 or more, even more preferably 1.7 or more, and preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 2.2 or less. Furthermore, the mass ratio of the content of the raw material olefin with double bond positions at positions 3 to 5 to the content of the raw material olefin with double bond positions at positions 6 to 8 in a 16-carbon olefin is (raw material olefin...) 3～5 Position / raw material olefins 6～8 The preferred value (position) is 1.0 to 4.0, more preferably 1.3 to 3.5, and even more preferably 1.7 to 2.2.

[0041] The content of α-olefins (with double bonds at position 1) that may inevitably exist in 16-carbon olefins is preferably less than 5.0% by mass, more preferably less than 3.0% by mass, and even more preferably less than 2.5% by mass. Alternatively, α-olefins are preferably not present in 16-carbon olefins.

[0042] Furthermore, the aforementioned 16-carbon olefin can be obtained by isomerization (double bond shifting) of a 1-position double bond olefin (α-olefin) generated from the dehydration reaction of a 16-carbon alcohol. Specifically, relative to 100 parts by mass of 1-hexadecaneol, the amount of a solid acid catalyst such as alumina added is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and preferably 15 parts by mass or less, more preferably 10 parts by mass or less. In addition, the amount added is preferably 0.5 to 15 parts by mass, more preferably 2 to 10 parts by mass.

[0043] Next, the isomerization reaction is carried out under stirring at a temperature preferably above 220°C, more preferably above 260°C, and more preferably below 350°C, and preferably between 220°C and 350°C, and more preferably between 260°C and 350°C, for a period of at least 1 hour, more preferably at least 3 hours, and preferably less than 30 hours, and more preferably less than 10 hours, and preferably between 1 and 30 hours, and more preferably between 3 and 10 hours. By appropriately distilling the product after the reaction, the aforementioned 16-carbon olefin can be obtained.

[0044] The content of sulfonic acid or its salt containing sulfonic acid or its salt containing sulfonic acid or its salt with sulfonic acid group present at position 1 to 4 in component (A), obtained by sulfonating the above-mentioned raw material olefin with 16 carbon atoms, is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 68% by mass or less in component (A). Furthermore, the content of sulfonic acid or its salt containing sulfonic acid or its salt containing sulfonic acid or its salt with sulfonic acid group present at position 1 to 4 in component (A) is preferably 40% by mass or more than 75% by mass or less, more preferably 50 to 70% by mass, and even more preferably 55 to 68% by mass.

[0045] When component (A) is sodium alkylene sulfonate with 16 carbon atoms, the content of sodium alkylene sulfonate with sulfonic acid groups at positions 1 to 4 in the sodium alkylene sulfonate with 16 carbon atoms is the same as described above.

[0046] The content of the sulfonic acid or its salt containing a sulfonic acid group at the 2-position in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably 10% by mass or more, more preferably 13% by mass or more, even more preferably 17% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. Furthermore, the content of the sulfonic acid or its salt containing a 16-carbon olefin sulfonic acid or its salt in component (A) is preferably 10% by mass or more and 35% by mass or less, more preferably 13 to 30% by mass, and even more preferably 17 to 25% by mass.

[0047] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of sodium olefin sulfonate with sulfonic acid groups at position 2 in sodium olefin sulfonate with 16 carbon atoms is the same as described above.

[0048] The content of the sulfonic acid or its salt containing a sulfonic acid group at the 3-position in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably 5% by mass or more, more preferably 11% by mass or more, even more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Furthermore, the content of the sulfonic acid or its salt containing a 16-carbon olefin sulfonic acid or its salt in component (A) is preferably 5% by mass or more, 30% by mass, more preferably 11 to 25% by mass, and even more preferably 15 to 20% by mass in component (A).

[0049] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of sodium olefin sulfonate with sulfonic acid groups at position 3 in sodium olefin sulfonate with 16 carbon atoms is the same as described above.

[0050] The content of the sulfonic acid or its salt containing a sulfonic acid group at the 4-position in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably 15% by mass or more, more preferably 18% by mass or more, even more preferably 19% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 23% by mass or less in component (A). Furthermore, the content of the sulfonic acid or its salt containing a 16-carbon olefin sulfonic acid or its salt containing a sulfonic acid group at the 4-position in component (A) is preferably 15% by mass or more and 30% by mass or less, more preferably 18 to 25% by mass, and even more preferably 19 to 23% by mass in component (A).

[0051] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of sodium olefin sulfonate with sulfonic acid group at position 4 in sodium olefin sulfonate with 16 carbon atoms is the same as above.

[0052] Furthermore, the content of sulfonic acid or its salt with a sulfonic acid group present at the 1-position in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably less than 5.0% by mass, more preferably less than 3.0% by mass, and even more preferably less than 2.5% by mass. Alternatively, the 16-carbon olefin sulfonic acid or its salt in component (A) preferably does not contain sulfonic acid or its salt with a sulfonic acid group present at the 1-position.

[0053] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of sodium olefin sulfonate with sulfonic acid group present at position 1 in sodium olefin sulfonate with 16 carbon atoms is the same as described above, or preferably does not contain sodium olefin sulfonate with sulfonic acid group present at position 1.

[0054] In the 16-carbon olefin sulfonic acid or its salt of component (A), from the viewpoint of improving productivity and reducing impurities, the mass ratio (hydroxyl body / olefin body) of the content of hydroxyl body (HAS) to the content of olefin body (IOS) is preferably 50 / 50 to 100 / 0, more preferably 60 / 40 to 100 / 0, even more preferably 70 / 30 to 100 / 0, even more preferably 75 / 25 to 100 / 0, and even more preferably 75 / 25 to 95 / 5.

[0055] In addition, regarding the mass ratio (hydroxyl body / olefin body), the hydroxyl body and olefin body were separated from component (A) by HPLC (high performance liquid chromatography), and the peak areas of each component were obtained by placing them in MS. The mass ratio was then determined based on the HPLC-MS peak areas.

[0056] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the mass ratio (hydroxyl body / olefin body) of the content of hydroxyl body (HAS) to olefin body (IOS) in sodium olefin sulfonate with 16 carbon atoms is the same as above.

[0057] Component (A), an 16-carbon olefin sulfonic acid or its salt, is obtained by sulfonating a raw olefin. Therefore, unreacted raw olefins and inorganic compounds may remain in component (A). The lower the content of these components, the better. The same applies when component (A) is a 16-carbon olefin sulfonate sodium salt.

[0058] The content of unreacted raw material olefin in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably less than 5.0% by mass, more preferably less than 3.0% by mass, even more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass.

[0059] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of unreacted raw material olefin in sodium olefin sulfonate with 16 carbon atoms is the same as described above.

[0060] The content of inorganic compounds in the 16-carbon olefin sulfonic acid or its salt in component (A) is preferably less than 7.5% by mass, more preferably less than 5.0% by mass, even more preferably less than 3.0% by mass, even more preferably less than 2.0% by mass, and even more preferably less than 1.6% by mass.

[0061] When component (A) is sodium olefin sulfonate with 16 carbon atoms, the content of inorganic compounds in sodium olefin sulfonate with 16 carbon atoms is the same as described above.

[0062] From the viewpoint of effectively promoting excellent shampooing results, the content of ingredient (A) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and even more preferably 1% by mass or more. Furthermore, from the viewpoint of ensuring good low-temperature stability, the content of ingredient (A) in the hair-cleansing composition of the present invention is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and even more preferably 10% by mass or less. Moreover, the content of ingredient (A) in the hair-cleansing composition of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, further preferably 0.1 to 12% by mass, and even more preferably 1 to 10% by mass.

[0063] The 16-carbon olefin sulfonic acid or its salt of component (A) can be obtained by reacting the above-mentioned 16-carbon olefin with sulfur trioxide to obtain it. Specifically, it can be obtained by sulfonating the olefin, neutralizing it, and then hydrolyzing it.

[0064] More specifically, from the viewpoints of increasing the yield of component (A) and improving reactivity, the amount of sulfur trioxide used during the sulfonation of the feedstock olefin is preferably 0.8 mol or more, more preferably 0.9 mol or more, and even more preferably 0.95 mol or more, relative to 1 mole of the feedstock olefin. Furthermore, from the viewpoints of economy and suppressing unnecessary coloring of component (A), the amount of sulfur trioxide used during the sulfonation of the feedstock olefin is preferably 1.2 mol or less, more preferably 1.1 mol or less, and even more preferably 1.05 mol or less. Moreover, the amount of sulfur trioxide used during the sulfonation of the feedstock olefin is preferably 0.8 to 1.2 mol, more preferably 0.9 to 1.1 mol, and even more preferably 0.95 to 1.05 mol, relative to 1 mole of the feedstock olefin.

[0065] From the viewpoint of preventing the solidification of sulfur trioxide and component (A), the reaction temperature for sulfonating the above-mentioned raw material olefin is preferably 0°C or higher. Furthermore, from the viewpoint of suppressing unnecessary coloring of component (A), the reaction temperature is preferably 50°C or lower. Moreover, the reaction temperature for sulfonating the raw material olefin is preferably 0 to 50°C.

[0066] During neutralization, it reacts with basic compounds such as sodium hydroxide, potassium hydroxide, ammonia, and 2-aminoethanol. From the viewpoint of suppressing the formation of impurities such as raw material olefins or inorganic salts, and from the viewpoint of improving reactivity, the amount of this basic compound added relative to 1 mole of sulfonic acid group is preferably 1.0 mole times or more, more preferably 1.03 mole times or more. Furthermore, from the viewpoint of economy, and from the viewpoint of suppressing the formation of impurities such as raw material olefins or inorganic salts, the amount of the basic compound added relative to 1 mole of sulfonic acid group is preferably 2.5 mole times or less, more preferably 2.0 mole times or less, and even more preferably 1.5 mole times or less. Moreover, relative to 1 mole of sulfonic acid group, the amount of the basic compound added is preferably 1.0 to 2.5 mole times, more preferably 1.03 to 2.0 mole times, and even more preferably 1.03 to 1.5 mole times.

[0067] From the viewpoint of suppressing the formation of impurities such as internal olefins or inorganic salts due to side reactions, the temperature at which the sulfonated raw material olefin is mixed with the basic compound during neutralization, and the reaction temperature, are preferably 40°C or lower, more preferably 35°C or lower, even more preferably 30°C or lower, and even more preferably 25°C or lower. From the viewpoint of improving reactivity, the temperature is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and even more preferably 20°C or higher. Furthermore, the temperature at which the sulfonated raw material olefin is mixed with the basic compound, and the reaction temperature, are preferably 0–40°C, more preferably 10–35°C, even more preferably 15–30°C, and even more preferably 20–25°C.

[0068] From the viewpoint of increasing reactivity in the presence of water, the reaction temperature for hydrolysis after neutralization is preferably 120°C or higher, more preferably 140°C or higher, and even more preferably 160°C or higher. Furthermore, from the viewpoint of suppressing product decomposition, the reaction temperature for hydrolysis is preferably 220°C or lower, more preferably 180°C or lower. Moreover, the reaction temperature for hydrolysis is preferably 120–220°C, more preferably 140–180°C, and even more preferably 160–180°C.

[0069] From the viewpoint of bringing the reaction to a complete stop, the reaction time during hydrolysis is preferably 30 minutes or more, more preferably 45 minutes or more. Furthermore, from the viewpoint of improving productivity, the reaction time during hydrolysis is preferably 240 minutes or less, more preferably 180 minutes or less, even more preferably 120 minutes or less, and even more preferably 90 minutes or less. Moreover, the reaction time during hydrolysis is preferably 30 to 240 minutes, more preferably 45 to 180 minutes, even more preferably 45 to 120 minutes, and even more preferably 45 to 90 minutes. These reactions can be carried out continuously. After the reaction is complete, purification can be performed by extraction, washing, or the like.

[0070] The hair-cleansing composition of the present invention contains a cationic polymer as component (B). Here, "cationic polymer" refers to a polymer having substituents that undergo cationization when dissolved in water. By containing this component (B), it can combine with the above-mentioned component (A) to achieve excellent shampooing effect and ensure good low-temperature stability.

[0071] Furthermore, the same applies when component (A) is sodium sulfonate with 16 carbon atoms.

[0072] As a component (B), specifically, one or more may be selected from cationic polygalactomannan, cationic hydroxyalkyl cellulose, diallyl quaternary ammonium salt polymer, copolymer containing methacrylamide propyltrimethylammonium chloride, and cross-linked cationic polymers.

[0073] As a cationic polygalactomannan, more specifically, one or more can be selected from cationic guar gum, cationic tara gum, and cationic locust bean gum.

[0074] As a cationic hydroxyalkyl cellulose, more specifically, one or two of cationic hydroxyethyl cellulose and cationic hydroxypropyl cellulose can be cited.

[0075] As a diallyl quaternary ammonium salt polymer, more specifically, examples include one or more selected from polydiallyl dimethyl ammonium chloride, diallyl dimethyl ammonium chloride / acrylic acid copolymer, diallyl dimethyl ammonium chloride / acrylamide copolymer, and diallyl dimethyl ammonium chloride / acrylic acid / acrylamide copolymer.

[0076] Examples of copolymers containing methacrylamide propyltrimethylammonium chloride include one or more selected from acrylic acid / methyl acrylate / methacrylamide propyltrimethylammonium chloride copolymer and acrylic acid / acrylamide / methacrylamide propyltrimethylammonium chloride copolymer.

[0077] As a cross-linked cationic polymer, more specifically, examples include N,N-dimethylaminoethyl methacrylate diethyl ester sulfate / N,N-dimethylacrylamide / polyethylene glycol dimethacrylate copolymer, etc.

[0078] From the viewpoint of balancing excellent shampooing effect and good low-temperature stability, it is preferred to select one or more of cationic hydroxyalkyl cellulose and cross-linked cationic polymers, and more preferably cationic hydroxyethyl cellulose.

[0079] From the viewpoint of effectively promoting excellent shampooing results, the content of ingredient (B) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more. Furthermore, from the viewpoint of ensuring good low-temperature stability, the content of ingredient (B) in the hair-cleansing composition of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, and even more preferably 0.8% by mass or less. Moreover, the content of ingredient (B) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05 to 5% by mass, more preferably 0.1 to 1% by mass, even more preferably 0.2 to 1% by mass, and even more preferably 0.2 to 0.8% by mass.

[0080] From the viewpoint of achieving good operability, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 1 or more, preferably 5 or more, more preferably 10 or more, and even more preferably 12 or more. Furthermore, from the viewpoint of effectively achieving excellent shampooing results, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 500 or less, preferably 100 or less, and even more preferably 80 or less. Moreover, the mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 1 or more and 500 or less, preferably 5 to 100, more preferably 10 to 80, and even more preferably 12 to 80.

[0081] From the viewpoint of further and more reliably combining with the above-mentioned ingredient (A) to achieve excellent shampooing effect and good low-temperature stability, the hair cleaning composition of the present invention may contain anionic surfactant (C) other than the above-mentioned ingredient (A).

[0082] As a component (C), specifically, one or more may be selected from sulfonates, amino acid salts, sulfosuccinates, sulfate esters, and carboxylates.

[0083] The sulfonate of component (C) refers to the sulfonate other than component (A). More specifically, examples of such sulfonate include one or more selected from aminoethyl sulfonates such as N-acylmethyl taurate, alkylbenzene sulfonates, alkenylbenzene sulfonates, alkane sulfonates, and α-olefin sulfonates having 14 carbon atoms.

[0084] As an amino acid salt, more specifically, it can be selected from one or more of acylglutamate salts, sarcosine derivatives, alanine derivatives, glycine derivatives, and arginine derivatives.

[0085] Examples of sulfosuccinates include one or more selected from alkyl sulfosuccinate salts and polyoxyalkylene sulfosuccinate alkyl ester salts.

[0086] Examples of sulfate ester salts include one or more selected from alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and polyoxyalkylene alkylphenyl ether sulfates.

[0087] Examples of carboxylates include one or more selected from fatty acid salts and polyoxyalkylene alkyl ether acetates.

[0088] From the viewpoint of balancing excellent shampooing effect and good low-temperature stability, the preferred choice is one or more selected from aminoethyl sulfonate, amino acid salt, sulfosuccinate, polyoxyalkylene alkyl ether sulfate, and polyoxyalkylene alkyl ether acetate; more preferably, one or more selected from aminoethyl sulfonate, amino acid salt, sulfosuccinate, and polyoxyalkylene alkyl ether sulfate; and even more preferably, aminoethyl sulfonate.

[0089] From the viewpoint of effectively promoting excellent shampooing results, the content of ingredient (C) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and even more preferably 1% by mass or more. Furthermore, from the viewpoint of ensuring good low-temperature stability, the content of ingredient (C) in the hair-cleansing composition of the present invention is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and even more preferably 9% by mass or less. Moreover, the content of ingredient (C) in the hair-cleansing composition of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, further preferably 0.1 to 12% by mass, and even more preferably 1 to 9% by mass.

[0090] When component (C) contains olefin sulfonic acid or its salt having a carbon number other than 16, from the viewpoint of improving the smoothness of the foam and low-temperature stability, the mass ratio of the content of component (A) in the hair cleaning agent composition of the present invention to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, and even more preferably 0.95 or more.

[0091] From the viewpoint of effectively achieving excellent shampooing results, the mass ratio (A) / (C) of component (A) to component (C) is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. Furthermore, from the viewpoint of effectively suppressing unnecessary precipitation of component (A) and exhibiting good low-temperature stability, the mass ratio (A) / (C) of component (A) to component (C) is preferably 100 or less, more preferably 25 or less, and even more preferably 15 or less. Moreover, the mass ratio (A) / (C) of component (A) to component (C) is preferably 0.01 to 100, more preferably 0.05 to 25, and even more preferably 0.1 to 15.

[0092] From the viewpoint of further and reliably combining with the above-mentioned component (A) to exert excellent shampooing effect and exhibit good low-temperature stability, the hair cleaning composition of the present invention may contain an amphoteric surfactant (D).

[0093] As component (D), specifically, one or more of carbonyl betaine and sulfobetaine may be selected. More specifically, one or more of carbonyl betaine and sulfobetaine may be selected from alkyl, alkenyl or acyl groups having 6 to 22 carbon atoms (preferably 8 to 18 carbon atoms).

[0094] Preferably, it is selected from one or more of lauramidopropyl betaine, coconut oil fatty acid amide propyl betaine, lauramidopropyl hydroxysulfonate betaine, and lauramidosulfonate betaine, and more preferably, it is selected from one or two of lauramidopropyl betaine and lauramidopropyl hydroxysulfonate betaine.

[0095] From the viewpoint of further improving the excellent shampooing effect, the content of ingredient (D) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, from the viewpoint of further reliably ensuring good low-temperature stability, the content of ingredient (D) in the hair-cleansing composition of the present invention is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. Moreover, the content of ingredient (D) in the hair-cleansing composition of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 15% by mass, and even more preferably 0.1 to 12% by mass.

[0096] From the viewpoint of effectively suppressing unnecessary precipitation of component (A) and exhibiting good low-temperature stability, the mass ratio (A) / (D) of component (A) to component (D) is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. Furthermore, from the viewpoint of effectively improving excellent shampooing performance, the mass ratio (A) / (D) of component (A) to component (D) is preferably 50 or less, more preferably 25 or less, and even more preferably 9 or less. Moreover, the mass ratio (A) / (D) of component (A) to component (D) is preferably 0.01 to 50, more preferably 0.05 to 25, and even more preferably 0.1 to 9.

[0097] From the viewpoint of further and more reliably combining with the above-mentioned ingredients to achieve excellent shampooing effect and good low-temperature stability, the hair cleaning composition of the present invention may contain a nonionic surfactant (E).

[0098] As a component (E), specifically, it may be selected from one or more of polyoxyalkylene alkyl ethers, fatty acid alkanolamides, alkyl glycosides, and alkyl glycerol ethers.

[0099] More specifically, examples of polyoxyalkylene alkyl ethers include those with 6 to 22 carbon atoms in the alkyl group, preferably 8 to 18 carbon atoms. Among these, polyoxyethylene alkyl ethers are preferred, more preferably those with an average addition molar number of oxyethylidene of 3 to 50, and even more preferably 4 to 16.

[0100] Examples of fatty acid alkanolamides include monoalkanolamides or dialkanolamides with 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.

[0101] Examples of alkyl glycosides include those with 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms.

[0102] Examples of alkyl glycerol ethers include those with 6 to 22 carbon atoms, preferably with 8 to 18 carbon atoms.

[0103] More preferably, it is a fatty acid alkanolamide.

[0104] From the viewpoint of further enhancing the excellent shampooing effect when combined with the aforementioned component (B), the content of component (E) in the hair-cleansing composition of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and even more preferably 0.5% by mass or more. Furthermore, from the viewpoint of effectively ensuring good low-temperature stability when combined with component (B), the content of component (E) in the hair-cleansing composition of the present invention is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and even more preferably 6% by mass or less. Moreover, the content of component (E) in the hair-cleansing composition of the present invention is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, even more preferably 0.1 to 8% by mass, and even more preferably 0.5 to 6% by mass.

[0105] From the viewpoint of effectively suppressing unnecessary precipitation of component (A) and exhibiting good low-temperature stability, the mass ratio of component (A) to component (E) ((A) / (E)) is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. Furthermore, from the viewpoint of also effectively achieving excellent shampooing results, the mass ratio of component (A) to component (E) ((A) / (E)) is preferably 50 or less, more preferably 25 or less, and even more preferably 9 or less. Moreover, the mass ratio of component (A) to component (E) ((A) / (E)) is preferably 0.01 to 50, more preferably 0.05 to 25, and even more preferably 0.1 to 9.

[0106] In addition to the above-mentioned components, the hair cleaning composition of the present invention may contain, to a extent that does not impair the effects of the present invention, water, a viscosity reducer, polyols, preservatives, and reducing agents, which may serve as a medium when sulfonating raw olefins to obtain component (A). Furthermore, it may contain other components commonly used as cosmetic ingredients. Examples of such components include touch enhancers, thickeners, fragrances, ultraviolet absorbers, visible light absorbers, chelating agents, antioxidants, colorants, preservatives, pH adjusters, viscosity modifiers, pearlescent agents, and humectants.

[0107] From the viewpoint of foaming during washing, the pH value of the hair-cleansing composition of the present invention at 25°C, as a 5% aqueous dispersion, is preferably 3.0 or higher, more preferably 3.2 or higher, and even more preferably 4.3 or higher. Furthermore, from the viewpoint of inhibiting tangling of hair, the pH value of the hair-cleansing composition of the present invention at 25°C, as a 5% aqueous dispersion, is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Moreover, the pH value of the hair-cleansing composition of the present invention at 25°C, as a 5% aqueous dispersion, is preferably 3.0 to 7.0, more preferably 3.2 to 6.5, and even more preferably 4.3 to 6.0.

[0108] The hair-cleansing composition of the present invention typically contains an aqueous medium. Examples of aqueous mediums include: water; lower alcohols such as ethanol and isopropanol; low molecular weight diols and triols with 6 or fewer carbon atoms, such as 1,3-butanediol, glycerol, ethylene glycol, and propylene glycol; water is preferred. The content of the aqueous medium can be appropriately selected according to the dosage form of the hair-cleansing composition, and is typically 5 to 99% by mass, preferably 30 to 98% by mass.

[0109] Thus, when the hair cleaning composition of the present invention is applied to hair, it exhibits the following properties: it provides good foaming properties and smooth foam during washing, and the hair feels genuinely soft during rinsing; and it has excellent low-temperature stability.

[0110] Therefore, the hair-cleansing composition of the present invention is also highly useful as a method for washing hair. Specifically, this hair-washing method involves, for example, pre-wetting the hair with water, applying the hair-cleansing composition of the present invention to the hair and washing it, followed by rinsing with water.

[0111] Furthermore, if the hair cleaning agent composition of the present invention is used, the low-temperature stabilization method for the hair cleaning agent composition is also highly useful.

[0112] Regarding the above embodiments, the present invention further discloses the following hair cleaning agent composition.

[0113] [1] A hair cleaning composition comprising the following ingredients (A) and (B):

[0114] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0115] (B) Cationic polymers,

[0116] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0117] [2] In the hair cleaning composition described in [1] above, the average double bond position of the raw material olefin having 16 carbon atoms forming component (A) is preferably 4.0 or more, more preferably 4.1 or more, and preferably 4.4 or less, more preferably 4.2 or less.

[0118] [3] The hair cleaning agent composition as described in [1] or [2] above, wherein the content of the raw material olefin with the double bond position at position 2 in the raw material olefin having the number of carbon atoms is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 35% by mass or less, more preferably 32% by mass or less, even more preferably 24% by mass or less.

[0119] [4] The hair cleaning composition as described in any one of [1] to [3] above, wherein the content of the raw material olefin with the double bond position at position 3 in the raw material olefin having the number of carbon atoms is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 30% by mass or less, more preferably 24% by mass or less, even more preferably 19% by mass or less.

[0120] [5] The hair cleaning composition as described in any one of [1] to [4] above, wherein the content of the olefin with the double bond position at position 4 in the olefin having 16 carbon atoms is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 17% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 19% by mass or less.

[0121] [6] The hair cleaning agent composition as described in any one of [1] to [5] above, wherein the content of the raw material olefin with the double bond position at position 5 in the raw material olefin having the number of carbon atoms is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 13% by mass or more, and preferably 25% by mass or less, more preferably 19% by mass or less, even more preferably 15% by mass or less.

[0122] [7] The hair cleaning composition as described in any one of [1] to [6] above, wherein the content of the raw material olefin with the double bond position at position 6 in the raw material olefin having the number of carbon atoms is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 11% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 13% by mass or less.

[0123] [8] The hair cleaning composition as described in any one of [1] to [7] above, wherein the total content of the raw material olefins with double bond positions at the 7th or 8th position in the raw material olefins having the number of carbon atoms is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 12% by mass or more, and preferably 25% by mass or less, more preferably 22% by mass or less, and further preferably 16% by mass or less.

[0124] [9] The hair cleaning composition as described in any one of [1] to [8] above, wherein the content of the sulfonic acid group in the 16-carbon olefin sulfonic acid or its salt in component (A) being present at position 1 to position 4 or less is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, further preferably 68% by mass or less.

[0125]

[10] The hair cleaning composition as described in any one of [1] to [9] above, wherein the content of the sulfonic acid group of the 16-carbon olefin sulfonic acid or its salt in component (A) having a sulfonic acid group at the 2-position is preferably 10% by mass or more, more preferably 13% by mass or more, further preferably 17% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less.

[0126]

[11] The hair cleaning composition as described in any one of [1] to

[10] above, wherein the content of the sulfonic acid group of the 16-carbon olefin sulfonic acid or its salt in component (A) having a sulfonic acid group at the 3-position is preferably 5% by mass or more, more preferably 11% by mass or more, further preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less.

[0127]

[12] The hair cleaning composition as described in any one of [1] to

[11] above, wherein the mass ratio (hydroxyl body / olefin body) of the content of hydroxyl body (HAS) to the content of olefin body (IOS) in the 16-carbon olefin sulfonic acid or its salt of component (A) is preferably 50 / 50 to 100 / 0, more preferably 60 / 40 to 100 / 0, even more preferably 70 / 30 to 100 / 0, even more preferably 75 / 25 to 100 / 0, and even more preferably 75 / 25 to 95 / 5.

[0128]

[13] The hair cleaning composition as described in any one of [1] to

[12] above, wherein the content of component (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, even more preferably 10% by mass or less.

[0129]

[14] The hair cleaning composition as described in any one of [1] to

[13] above, wherein component (B) is preferably one or more cationic polymers selected from cationic polygalactomannan, cationic hydroxyalkyl cellulose, diallyl quaternary ammonium salt polymer and cross-linked cationic polymer, more preferably one or more selected from cationic hydroxyalkyl cellulose and cross-linked cationic polymer, and even more preferably cationic hydroxyethyl cellulose.

[0130]

[15] The hair cleaning composition as described in any one of [1] to

[14] above, wherein the content of component (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.8% by mass or less.

[0131]

[16] The hair cleaning composition as described in any one of [1] to

[15] above, wherein the mass ratio of the content of component (A) to the content of component (B) (A) / (B) is preferably 5 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 100 or less, more preferably 80 or less.

[0132]

[17] The hair cleaning composition as described in any one of [1] to

[16] above, wherein the 16-carbon olefin sulfonic acid or its salt thereof of component (A) is sodium olefin sulfonate with a carbon number of 16.

[0133]

[18] In any of the above-described hair cleaning composition [1] to

[17] , when component (C) contains an olefin sulfonic acid or a salt thereof with a carbon number other than 16, the mass ratio of the content of component (A) in the hair cleaning composition to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more.

[0134]

[19] Use of a hair cleaning composition comprising the following ingredients (A) and (B):

[0135] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0136] (B) Cationic polymers,

[0137] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0138]

[20] The use of the hair cleaning composition as described in

[19] above, wherein, when component (C) contains an olefin sulfonic acid or a salt thereof with a carbon number other than 16, the mass ratio of the content of component (A) in the hair cleaning composition to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more.

[0139]

[21] A method for washing hair, wherein a hair-cleansing composition comprising the following ingredients (A) and (B) is applied to the hair:

[0140] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0141] (B) Cationic polymers,

[0142] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0143]

[22] In the hair washing method described above

[21] , when the component (C) contains an olefin sulfonic acid or a salt thereof with a carbon number other than 16, the mass ratio of the content of component (A) in the hair cleaning agent composition to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more.

[0144]

[23] A method for low-temperature stabilization of a hair cleaning agent composition, which utilizes the hair cleaning agent composition described below, the hair cleaning agent composition containing the following components (A) and (B):

[0145] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0146] (B) Cationic polymers,

[0147] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0148]

[24] In the low-temperature stabilization method of the hair cleaning agent composition as described in

[23] above, when the component (C) contains an olefin sulfonic acid or a salt thereof with a carbon number other than 16, the mass ratio of the content of component (A) in the hair cleaning agent composition to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more.

[0149]

[25] Use of a hair cleaning composition for achieving low-temperature stabilization, the hair cleaning composition comprising the following components (A) and (B):

[0150] (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 3.9 to 4.5.

[0151] (B) Cationic polymers,

[0152] The mass ratio of the content of component (A) to the content of component (B) (A) / (B) is more than 1 and less than 500.

[0153]

[26] As described above in

[25] for achieving low-temperature stabilization, wherein when component (C) contains an olefin sulfonic acid or a salt thereof with a carbon number other than 16, the mass ratio of the content of component (A) in the hair cleaning agent composition to the total amount of olefin sulfonic acid or its salt ((A) / (total amount of olefin sulfonic acid or its salt)) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, even more preferably 0.8 or more, even more preferably 0.85 or more, even more preferably 0.9 or more, even more preferably 0.95 or more.

[0154] [Example]

[0155] The present invention will now be specifically described based on embodiments. Furthermore, in the tables, unless otherwise specified, the content of each component is expressed as a percentage by mass.

[0156] In addition, the methods for determining various physical properties are described below.

[0157] [Methods for determining various physical properties]

[0158] (i) Method for determining the double bond position of the feed olefin

[0159] The double bond positions of the starting olefin were determined using gas chromatography (GC). Specifically, after reacting the starting olefin with dimethyl disulfide to prepare a disulfide derivative, the components were separated using GC. The double bond positions of the starting olefin were then determined from the peak areas of each component.

[0160] In addition, the apparatus and analytical conditions used for the determination are described below. GC apparatus (trade name: HP6890, manufactured by Hewlett Packard), column (trade name: Ultra-Alloy-1HT capillary column 30m × 250μm × 0.15μm, manufactured by Frontier Laboratories), detector (flame ionization detector (FID)), injection temperature 300°C, detector temperature 350°C, He flow rate 4.6 mL / min.

[0161] (ii) Determination of the content of sodium sulfonate corresponding to the position of sulfonic acid group in the olefinic group

[0162] The content of sodium sulfonates containing sulfonic acid groups was determined by high-performance liquid chromatography-mass spectrometry (HPLC-MS) corresponding to the bonding positions of these sulfonic acid groups. Specifically, the hydroxyl groups containing sulfonic acid groups were separated by HPLC and identified separately by MS. The content of each was then determined from the HPLC-MS peak areas.

[0163] In addition, the apparatus and conditions used for the determination are described below. HPLC apparatus LD20ASXR (manufactured by Shimadzu Corporation); column ODS Hypersil (registered trademark), (4.6 × 250 mm, particle size: 3 μm, Thermo Fisher Scientific (manufactured); Sample preparation (diluted 1000 times with methanol); Eluent A (water with 10 mM ammonium acetate); Eluent B (methacrylonitrile / water = 95 / 5 (v / v) solution with 10 mM ammonium acetate); Gradient (0 min (A / B = 60 / 40) → 15.1–20 min (30 / 70) → 20.1–30 min (60 / 40); MS apparatus LCMS-2020 (manufactured by Shimadzu Corporation); ESI detection (anion detection m / z: 321.10 (component with 16 or 18 carbon atoms (A))), column temperature (40 °C), flow rate (0.5 mL / min), injection volume (5 μL).

[0164] (iii) Method for determining the mass ratio of hydroxyl body to olefin body

[0165] The mass ratio of hydroxyl to olefin bodies in sodium olefin sulfonate was determined by HPLC-MS. Specifically, the hydroxyl and olefin bodies were separated by HPLC and identified separately by MS. The ratio of each was then calculated from the HPLC-MS peak areas.

[0166] In addition, the apparatus and conditions used for the determination are as follows: HPLC apparatus (trade name: Agilent Technology 1100, manufactured by Agilent Technology Corporation), column (trade name: L-columnODS 4.6×150mm, manufactured by the Institute for Chemical Substance Evaluation, Inc.); sample preparation (diluted 1000 times with methanol); eluent A (water with 10 mM ammonium acetate added); eluent B (methanol with 10 mM ammonium acetate added); gradient (0 min (A / B = 30 / 70%) → 10 min (30 / 70%) → 55 min (0 / 100%) → 65 min (0 / 100%) → 66 min (30 / 70%) → 75 min (30 / 70%)); MS apparatus (trade name: Agilent Technology 1100MS SL (G1946D)); MS detection (anion detection m / z 60-1600, UV 240 nm).

[0167] (iv) Method for determining the content of olefins in raw materials

[0168] The content of unreacted olefins in sodium olefin sulfonate was determined by GC. Specifically, ethanol and petroleum ether were added to an aqueous solution of sodium olefin sulfonate, followed by extraction to obtain the olefins in the petroleum ether phase. The olefin content was then quantified by the GC peak area.

[0169] In addition, the apparatus and analytical conditions used for the determination are described below. GC apparatus (trade name: Agilent Technology 6850, manufactured by Agilent Technology); column (trade name: Ultra-Alloy-1HT capillary column 15m × 250μm × 0.15μm, manufactured by Frontier Laboratories); detector (flame ionization detector (FID)), injection temperature 300°C, detector temperature 350°C, He flow rate 3.8 mL / min.

[0170] (v) Methods for determining the content of inorganic compounds

[0171] The content of inorganic compounds is determined by potentiometric titration or neutralization titration. Specifically, the content of Na₂SO₄ is determined by potentiometric titration to calculate the sulfate (SO₄) content. 2-The content of NaOH is quantified by titration with dilute hydrochloric acid after neutralization.

[0172] [Manufacturing Example a1: Manufacturing of 16-carbon olefin a1]

[0173] 7000 g (28.9 mol) of 1-hexadecaneol (product name: KALCOL 6098, manufactured by Kao Corporation) and 350 g (5% by mass relative to the starting alcohol) of γ-alumina (manufactured by STREM Chemicals, Inc.) as a solid acid catalyst were added to a flask equipped with a stirrer. The reaction was carried out at 280°C with nitrogen gas flowing through the system (7000 mL / min) for 8 hours. The alcohol conversion rate was 100% at the end of the reaction. The obtained crude olefin was transferred to a distillation flask and distilled at 136–160°C / 4.0 mmHg to obtain a 16-carbon starting olefin a1 with 100% olefin purity. The double bond distribution of the obtained raw material olefin a1 is as follows: 1.8 wt% at C1 position, 21.8 wt% at C2 position, 18.7 wt% at C3 position, 18.6 wt% at C4 position, 14.3 wt% at C5 position, 11.4 wt% at C6 position, and a total of 13.6 wt% at C7 and C8 positions, with an average double bond position of 4.17.

[0174] [Manufacturing Example a2: Manufacturing of 16-carbon olefin a2]

[0175] The reaction time was changed to 7.5 hours, and otherwise, a 16-carbon olefin with 100% olefin purity, a raw material olefin a2, was obtained in the same manner as in manufacturing example a1. The double bond distribution of the obtained raw material olefin a2 was as follows: 2.4 wt% at C1, 23.2 wt% at C2, 18.7 wt% at C3, 18.2 wt% at C4, 13.9 wt% at C5, 11.2 wt% at C6, and a total of 12.4 wt% at C7 and C8, with an average double bond position of 4.08.

[0176] [Manufacturing Example a3: Manufacturing of 16-carbon olefin a3]

[0177] The reaction time was changed to 8.5 hours, and otherwise, a 16-carbon olefin with 100% olefin purity, a raw material olefin a3, was obtained in the same manner as in manufacturing example a1. The double bond distribution of the obtained raw material olefin a3 was as follows: C1 position 2.3 wt%, C2 position 20.7 wt%, C3 position 16.8 wt%, C4 position 17.5 wt%, C5 position 14.7 wt%, C6 position 12.9 wt%, and the total of C7 and C8 positions 15.2 wt%, with an average double bond position of 4.28.

[0178] [Manufacturing Example a4: Manufacturing of 16-carbon olefin a4]

[0179] The reaction time was changed to 6 hours, and otherwise, a 16-carbon olefin a4 with 100% olefin purity was obtained in the same manner as in manufacturing example a1. The double bond distribution of the obtained olefin a4 was as follows: C1 position 2.4 wt%, C2 position 31.8 wt%, C3 position 23.7 wt%, C4 position 16.9 wt%, C5 position 10.3 wt%, C6 position 7.1 wt%, and the combined C7 and C8 positions 7.9 wt%, with an average double bond position of 3.58.

[0180] [Manufacturing Example a5: Manufacturing of a5, a raw material olefin with 16 carbon atoms]

[0181] The reaction time was changed to 11 hours, and otherwise, a 16-carbon olefin a5 with 100% olefin purity was obtained in the same manner as in manufacturing example a1. The double bond distribution of the obtained olefin a5 was as follows: 0.4 wt% at C1, 15.4 wt% at C2, 13.8 wt% at C3, 15.3 wt% at C4, 18.5 wt% at C5, 15.0 wt% at C6, and a total of 21.6 wt% at C7 and C8, with an average double bond position of 4.78.

[0182] [Manufacturing Example a6: Manufacturing of 18-carbon olefin a6]

[0183] 7000 g (25.9 mol) of 1-octadecanool (product name: KALCOL 8098, manufactured by Kao Corporation) and 700 g (10% by mass relative to the starting alcohol) of γ-alumina (manufactured by STREM Chemicals, Inc.) as a solid acid catalyst were added to a flask equipped with a stirrer. The reaction was carried out at 280°C with nitrogen gas flowing through the system (7000 mL / min) for 11 hours. The alcohol conversion rate was 100% at the end of the reaction. The obtained crude olefin was transferred to a distillation flask and distilled at 148–158°C / 0.5 mmHg to obtain a 18-carbon starting olefin a6 with 100% olefin purity. The double bond distribution of the obtained raw material olefin a6 is as follows: 1.8 wt% at C1, 26.4 wt% at C2, 21.1 wt% at C3, 17.5 wt% at C4, 11.7 wt% at C5, 8.3 wt% at C6, 5.9 wt% at C7, and a total of 7.4 wt% at C8 and C9, with an average double bond position of 4.00.

[0184] [Manufacturing Example 1: Manufacturing of Sodium Alkene Sulfonate A1 with 16 Carbon Atoms]

[0185] The raw material olefin a1 obtained in manufacturing example a1 was placed in a jacketed membrane sulfonation reactor. Cooling water at 10°C was circulated through the outer jacket of the reactor, and the sulfonation reaction was carried out using sulfur trioxide gas under these conditions. The molar ratio of SO3 to internal olefin during the sulfonation reaction was set to 1.01. The obtained sulfonate was mixed with an alkaline aqueous solution prepared from sodium hydroxide (alkali) in an amount 1.04 molar times the theoretical acid value, and neutralized at 30°C for 1 hour using a continuous method. The obtained neutralized product was heated at 170°C for 1 hour in an autoclave to perform hydrolysis, thereby obtaining sodium sulfonate A1 with 16 carbon atoms. The obtained sodium sulfonate A1 with 16 carbon atoms contained 0.4% by mass of the raw material olefin and 0.39% by mass of inorganic compounds.

[0186] [Manufacturing Example 2: Manufacturing of Sodium A2, an Intra-olefin Sulfonate with 16 Carbon Atoms]

[0187] Using the raw material olefin a2 obtained in Manufacturing Example a2 as the raw material olefin, sodium sulfonate A2 with 16 carbon atoms was obtained in the same manner as in Manufacturing Example 1. The obtained sodium sulfonate A2 with 16 carbon atoms contained 0.7% by mass of raw material olefin and 0.49% by mass of inorganic compound.

[0188] [Manufacturing Example 3: Manufacturing of Sodium A3, an Intra-olefin Sulfonate with 16 Carbon Atoms]

[0189] Using the raw material olefin a3 obtained in Manufacturing Example a3 as the raw material olefin, sodium sulfonate A3 with 16 carbon atoms was obtained in the same manner as in Manufacturing Example 1. The obtained sodium sulfonate A3 with 16 carbon atoms contained 0.5% by mass of the raw material olefin and 0.54% by mass of inorganic compounds.

[0190] [Manufacturing Example 4: Manufacturing of Sodium A4, an Intra-olefin Sulfonate with 16 Carbon Atoms]

[0191] Using the raw material olefin a4 obtained in Manufacturing Example a4 as the raw material olefin, sodium sulfonate A4 with 16 carbon atoms was obtained in the same manner as in Manufacturing Example 1. The obtained sodium sulfonate A4 with 16 carbon atoms contained 0.4% by mass of the raw material olefin and 0.42% by mass of inorganic compounds.

[0192] [Manufacturing Example 5: Manufacturing of Sodium A5, an Intra-olefin Sulfonate with 16 Carbon Atoms]

[0193] Using the raw material olefin a5 obtained in Manufacturing Example a5 as the raw material olefin, sodium sulfonate A5 with 16 carbon atoms was obtained in the same manner as in Manufacturing Example 1. The obtained sodium sulfonate A5 with 16 carbon atoms contained 0.2% by mass of the raw material olefin and 0.43% by mass of inorganic compounds.

[0194] [Manufacturing Example 6: Manufacturing of Sodium A6, an 18-carbon-number internal olefin sulfonate]

[0195] Using the raw material olefin a6 obtained in Manufacturing Example a6 as the raw material olefin, sodium sulfonate A6 with 18 carbon atoms was obtained in the same manner as in Manufacturing Example 1. The obtained sodium sulfonate A6 with 18 carbon atoms contained 0.5% by mass of the raw material olefin and 0.45% by mass of inorganic compounds.

[0196] The physical properties of the obtained raw material olefins a1 to a6 and sodium sulfonate A1 to A6 are shown in Tables 1 to 2.

[0197] [Table 1]

[0198]

[0199] [Table 2]

[0200]

[0201] [Examples 1-16, Comparative Examples 1-7]

[0202] Using the obtained sodium olefin sulfonate A1 to A6, or sodium α-olefin sulfonate A7 with 14 carbon atoms (LIPOLANLB-400, manufactured by Lion Corporation), hair-cleansing compositions with the compositions shown in Tables 3 to 6 were prepared by conventional methods. Specifically, components (A), (B), and appropriate amounts of water, as well as component (C) added as needed, were placed in a beaker, heated to 60°C to mix, cooled to room temperature, and water was added. The pH was adjusted to 5.6 using a pH adjuster (succinic acid, or an aqueous solution of disodium succinate) to obtain each hair-cleansing composition.

[0203] The obtained hair cleaning agent composition was evaluated according to the following methods.

[0204] The results are shown in Tables 3-6.

[0205] <Shampoo effect evaluation>

[0206] Place the following ingredients in a beaker, heat to 80°C and mix. Once the mixture is completely dissolved, cool it to obtain a regular shampoo.

[0207] (Composition of a regular shampoo)

[0208]

[0209] A 20g bundle of untreated Japanese hair, 20cm in length, was washed with the aforementioned common shampoo to obtain a hair bundle for foaming performance evaluation. The obtained hair bundle was thoroughly wetted with warm water at 35-40°C, and 1g of each hair-cleansing agent composition was applied to the hair, followed by rinsing for 1 minute. Five professional sensory inspectors evaluated the hair bundle according to the following criteria, scoring each item for "good foaming performance," "smooth foam," and "softness of hair" during rinsing, and calculated the average score.

[0210] In addition, the average score of "3" is set as the standard and used as the evaluation index. If the average score of the five sensory examiners is 3 or above, it is judged as "pass".

[0211] 7: Very good.

[0212] 6: Very good.

[0213] 5: Good.

[0214] 4: Slightly better.

[0215] 3: Standards.

[0216] 2: Poor.

[0217] 1: Very bad.

[0218] <Evaluation of Low Temperature Stability>

[0219] The obtained hair cleaning agent compositions were placed in screw-top bottles and stored in a constant temperature bath at -5°C. Next, the presence or absence of precipitates over time was visually confirmed and evaluated according to the following criteria.

[0220] a: Even after 6 hours, no precipitates were found to form.

[0221] b: Precipitates were found to form during a period of more than 5 hours but less than 6 hours.

[0222] c: Precipitates were found to have formed after less than 5 hours.

[0223]

[0224]

[0225]

[0226] [Table 6]

[0227]

[0228] ※1, 3: Same as Table 3.

[0229] ※10: DIAPON K-SF, manufactured by Nippon Yushi Co., Ltd.

[0230] ※11: SOFTAZLINE LSB-R, manufactured by Kawaken Fine Chemicals Co., Ltd. ※12: SOFTAZLINE LPB-R, manufactured by Kawaken Fine Chemicals Co., Ltd. ※13: EMULGEN 108, manufactured by Kao Corporation.

[0231] ※14: AMINON C-11S, manufactured by Kao Corporation.

[0232] ※15: AG-124, manufactured by Kao Corporation.

[0233] *16: PENETOL GE-EH, manufactured by Kao Corporation.

Claims

1. A hair-cleansing composition, wherein, It contains the following ingredients (A) and (B): (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 4.0 to 4.

4. (B) Cationic hydroxyethyl cellulose, The average double bond positions of the 16-carbon olefin are determined by the following equation (1). Equation (1): In equation (1): n is an integer representing the position of the double bond in a 16-carbon olefin, and its unit is position; Cn represents the content of 16-carbon olefins (100% by mass) in which the double bond exists at the n-position of the carbon atom. The unit is mass%. In component (A), the content of sulfonic acid or its salt in an inner olefin sulfonic acid having a sulfonic acid group present at position 1 to position 4 is 40% to 75% by mass. The content of component (A) is more than 1% by mass and less than 12% by mass. The content of component (B) is more than 0.1% by mass and less than 1% by mass. The mass ratio of the content of component (A) to the content of component (B) is between 12 and 80.

2. The hair cleaning composition as claimed in claim 1, wherein, In component (A), the content of sulfonic acid or its salt in an inner olefin sulfonic acid having a sulfonic acid group at position 1 to position 4 is 50% to 70% by mass.

3. The hair cleaning composition as claimed in claim 1, wherein, In component (A), the content of an inner olefinic acid or its salt having a sulfonic acid group present at the 2 position is more than 10% by mass and less than 35% by mass.

4. The hair-cleansing composition according to any one of claims 1 to 3, wherein, In component (A), the content of an inner olefinic acid or its salt having a sulfonic acid group present at the 3 position is more than 5% by mass and less than 30% by mass.

5. The hair-cleansing composition according to any one of claims 1 to 3, wherein, In component (A), the content of an inner olefinic acid or its salt having a sulfonic acid group present at position 4 is 15% by mass or more and 30% by mass or less.

6. The hair-cleansing composition according to any one of claims 1 to 3, wherein, The content of component (A) is more than 1% by mass and less than 10% by mass.

7. The hair-cleansing composition according to any one of claims 1 to 3, wherein, In component (A), the mass ratio of the content of the hydroxyl body of the alkene sulfonic acid or its salt to the content of the alkene body of the alkene sulfonic acid or its salt is 50 / 50 to 95 / 5.

8. The hair-cleansing composition according to any one of claims 1 to 3, wherein, The content of component (B) is more than 0.2% by mass and less than 1% by mass.

9. The hair-cleansing composition according to any one of claims 1 to 3, wherein, The content of component (B) is more than 0.2% by mass and less than 0.8% by mass.

10. The hair-cleansing composition according to any one of claims 1 to 3, wherein, The content of an inner olefinic acid or its salt with a sulfonic acid group present at position 1 is less than 3.0% by mass in component (A).

11. The hair-cleansing composition according to any one of claims 1 to 3, wherein, It also contains component (C), which is an anionic surfactant other than component (A). Component (C) contains an olefin sulfonic acid or a salt thereof that has 16 or fewer carbon atoms, and, The mass ratio of the content of component (A) to the total amount of olefin sulfonic acid or its salt is 0.95 or more.

12. A method for washing hair, wherein, The hair is pre-wetted with water, the hair cleaning agent composition according to any one of claims 1 to 11 is applied to the hair and washed, and then rinsed with water.

13. A method for low-temperature stabilization of a hair-cleansing composition, wherein, The hair cleaning composition contains the following ingredients (A) and (B): (A) A 16-carbon olefin sulfonic acid or its salt obtained by sulfonating a raw olefin with an average double bond position of 4.0 to 4.

4. (B) Cationic hydroxyethyl cellulose, The average double bond positions of the 16-carbon olefin are determined by the following equation (1). Equation (1): In equation (1): n is an integer representing the position of the double bond in a 16-carbon olefin, and its unit is position; Cn represents the content of 16-carbon olefins (100% by mass) in which the double bond exists at the n-position of the carbon atom. The unit is mass%. In component (A), the content of sulfonic acid or its salt in an inner olefin sulfonic acid having a sulfonic acid group present at position 1 to position 4 is 40% to 75% by mass. The content of component (A) is more than 1% by mass and less than 12% by mass. The content of component (B) is more than 0.1% by mass and less than 1% by mass. The mass ratio of the content of component (A) to the content of component (B) is between 12 and 80.

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