WO2014125940A1 - 内部オレフィンスルホン酸塩組成物 - Google Patents
内部オレフィンスルホン酸塩組成物 Download PDFInfo
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- WO2014125940A1 WO2014125940A1 PCT/JP2014/052258 JP2014052258W WO2014125940A1 WO 2014125940 A1 WO2014125940 A1 WO 2014125940A1 JP 2014052258 W JP2014052258 W JP 2014052258W WO 2014125940 A1 WO2014125940 A1 WO 2014125940A1
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- internal olefin
- olefin sulfonate
- mass
- component
- composition
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
Definitions
- the present invention relates to an internal olefin sulfonate composition useful as a base for a detergent, and a detergent composition containing an internal olefin sulfonate.
- anionic surfactants particularly alkyl sulfates and alkyl polyoxyalkylene sulfates are widely used as household and industrial cleaning components because of their excellent detergency and foaming power.
- an olefin sulfonate particularly an internal olefin sulfonate obtained from an internal olefin having a double bond inside the olefin chain rather than at the end as a raw material has been reported.
- Such an internal olefin sulfonate is generally obtained by reacting an internal olefin with a gaseous sulfur trioxide-containing gas for sulfonation, neutralizing the obtained sulfonic acid, and further hydrolyzing, for example, Patent Documents 1 to 3 disclose improved production methods.
- the internal olefin sulfonate thus obtained is known to have good biodegradability and the like, but with regard to basic performance as a cleaning agent including foamability and foam quality, alkylpolyoxyalkylene sulfate Compared with general-purpose surfactants such as ester salts, it is still not sufficient, and further improvements are desired.
- New added value such as foam quality and instantaneous foamability is also required.
- the bubbles are large at the time of washing, and the bubble density and bubble viscosity are low, so that it is possible to bring out a light foam quality and quickly spread the bubbles, and at the time of rinsing, the moment when the bubbles disappear instantly
- a surfactant composition that has a comfortable foaming property and facilitates comfortable cleaning and rinsing in a short time.
- Such added value is useful, for example, in hair shampoos and body cleansing materials.
- Patent Document 4 discloses a specific internal olefin sulfonic acid for the purpose of imparting solubilizing power, penetrating power, and interfacial tension reducing ability as a cleaning component. For example, when used as a shampoo, It is disclosed that the touch is excellent and the touch is improved.
- Patent Document 5 describes specific internal olefin sulfonates for the purpose of improving detergency and discloses application examples to shampoos and liquid soaps.
- Patent Document 6 discloses an oil recovery accelerator using a surfactant containing a plurality of internal olefin sulfonates having different carbon numbers.
- Patent Document 1 JP-A-01-272564 (Patent Document 2) JP-A 61-134366 (Patent Document 3) JP-A 60-32759 (Patent Document 4) JP-A-2003-81935 (Patent Document 5) US Pat. No. 5,078,916 (Patent Document 6) International Publication No. 2010/129051
- the present invention contains (A) an internal olefin sulfonate having 12 carbon atoms and (B) an internal olefin sulfonate having 14 carbon atoms, and the content mass ratio of the component (A) to the component (B) (A /
- the present invention relates to an internal olefin sulfonate composition in which B) is 10/90 to 90/10, and the total content of component (A) and component (B) is 60 to 100% by mass.
- the present invention provides an internal olefin sulfonate composition capable of sufficiently enhancing good foamability, light foam quality and instantaneous foaming properties, and a detergent composition containing the internal olefin sulfonate.
- the present inventor studied the chain length of the aliphatic chain of the internal olefin sulfonate, the ratio thereof, and other various conditions, and as a result, the internal olefin sulfonate having 12 carbon atoms and the internal olefin sulfonate having 14 carbon atoms. If the total content of these components is kept within a certain range while maintaining a certain ratio, the internal olefin sulfonic acid combines light foam quality and instantaneous foaming properties in addition to good foaming properties. The present inventors have found that a salt composition can be obtained and completed the present invention.
- large bubbles that enable quick foaming at the time of washing provide a light foam quality with low bubble density and foam viscosity, while instantly rinsing Not only can the foam be instantly defoamed so that it can be defoamed, it can be washed comfortably, but also after washing, when it is dried by wiping it with a towel, for example, it also has a residual feeling of cleaning agent. It is possible to provide a cleaning composition containing an internal olefin sulfonic acid salt composition and an internal olefin sulfonic acid, which can sufficiently provide a good feel without any problems.
- the internal olefin sulfonate composition of the present invention contains (A) an internal olefin sulfonate having 12 carbon atoms and (B) an internal olefin sulfonate having 14 carbon atoms, and the component (A) and the component (B ) Content mass ratio (A / B) is 10/90 to 90/10, and the total content of component (A) and component (B) is 60 to 100% by mass.
- the internal olefin sulfonate is a sulfonate obtained by sulfonating, neutralizing and hydrolyzing the internal olefin (olefin having a double bond inside the olefin chain) as a raw material as described above. It is. That is, when the internal olefin is sulfonated, ⁇ -sultone is quantitatively produced, and a part of ⁇ -sultone is converted into ⁇ -sultone and olefin sulfonic acid, and these are further converted to hydroxy in the neutralization / hydrolysis step.
- the internal olefin has a broad meaning including the case where a so-called ⁇ -olefin is contained in a trace amount, in which the position of the double bond is located at the 1st position of the carbon chain.
- ⁇ -olefin is contained in a trace amount, in which the position of the double bond is located at the 1st position of the carbon chain.
- the hydroxy group of the resulting hydroxyalkane sulfonate is inside the alkane chain
- the double bond of the olefin sulfonate is inside the olefin chain.
- the product obtained is mainly a mixture of these, and some of them have a hydroxyalkane sulfonate having a hydroxy group at the end of a small amount of carbon chain, or a double bond at the end of carbon chain.
- Olefin sulfonates may be included.
- each of these products and mixtures thereof are collectively referred to as internal olefin sulfonates.
- the hydroxyalkane sulfonate is referred to as an internal olefin sulfonate hydroxy form (hereinafter also referred to as HAS), and the olefin sulfonate is referred to as an internal olefin sulfonate olefin form (hereinafter referred to as IOS).
- HAS internal olefin sulfonate hydroxy form
- IOS internal olefin sulfonate olefin form
- the content ratio (A / B) of the component (A) to the component (B) in the internal olefin sulfonate composition of the present invention is 10/90 to 90/10. 25/75 to 90/10 are preferable, 50/50 to 90/10 are more preferable, 75/25 to 90/10 are more preferable, and 80/20 to 90 / 10 is more preferable.
- the content ratio (A / B) of the component (A) and the component (B) in the internal olefin sulfonate composition of the present invention is preferably 10/90 to 80/20 from the viewpoint of foamability. 10/90 to 70/30 is more preferable, 10/90 to 30/70 is still more preferable, and 10/90 to 20/80 is still more preferable.
- the mass ratio (A / B) of component (A) and component (B) in the internal olefin sulfonate composition is a numerical value measured by a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS). is there. Specifically, the internal olefin sulfonate having 12 carbon atoms and the internal olefin sulfonate having 14 carbon atoms are separated by HPLC, and each is identified by subjecting to MS. The content mass ratio (A / B) of the component (A) and the component (B) of the internal olefin sulfonate is determined from the HPLC-MS peak area.
- the total content of the component (A) and the component (B) in the internal olefin sulfonate composition of the present invention is 60 to 100% by mass, and the foaming property, lightness of foam quality, and instantaneous foam breakage
- the lower limit of the total content of the component (A) and the component (B) is more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more from the viewpoint of the properties and the feel after drying.
- 95 mass% or more is more preferable, 96.5 mass% or more is further more preferable, and 97 mass% or more is still more preferable.
- the sulfonic acid group in the internal olefin sulfonate of the present invention is present inside the olefin chain or alkane chain, as is apparent from the above production method.
- the internal position where the position of the sulfonic acid group is present at the 2-position of the olefin chain or alkane chain is preferable that the content of olefin sulfonate is low and the content of internal olefin sulfonate present in the interior is higher.
- the content of the internal olefin sulfonate having a sulfonic acid group located at the 2-position of the olefin chain or alkane chain is low. Is more preferable.
- the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position in the internal olefin sulfonate of 12 and 14 carbon atoms (component (A) and component (B)) of the present invention is light foam, And from the point of instantaneous foaming property, 28 mass% or less is preferable in the total content of a component (A) and a component (B), it is more preferable that it is less than 25 mass%, and it is 23 mass% or less. More preferably, it is more preferably 22% by mass or less.
- the content of the internal olefin sulfonate in which the sulfonic acid group is present at the 2-position in the component (A) and the component (B) is the sum of the component (A) and the component (B) from the viewpoint of cost and productivity. 5 mass% or more is preferable in content, 7 mass% or more is more preferable, 15 mass% or more is more preferable, and 19 mass% or more is still more preferable.
- the content of the internal olefin sulfonate in which the sulfonic acid group is present at the 2-position in the component (A) and the component (B) is, among these viewpoints, the total content of the component (A) and the component (B).
- the content of the ⁇ -olefin sulfonate having the sulfonic acid group located at the 1-position of the olefin chain or alkane chain is determined from the viewpoint of light foam quality and instantaneous foaming properties.
- the total content of component (B) are preferably less than 2.8% by mass, and more preferably 2.0% by mass or less.
- the content of the ⁇ -olefin sulfonate having the sulfonic acid group at the 1-position of the olefin chain or alkane chain is the total content of component (A) and component (B) from the viewpoint of cost and productivity.
- the content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.3% by mass or more. Summing up these viewpoints, the content of the ⁇ -olefin sulfonate in which the position of the sulfonic acid group is located at the 1-position of the olefin chain or alkane chain is the total content of component (A) and component (B). Furthermore, 0.01 mass% or more and less than 2.8 mass% is more preferable, 0.1 mass% or more and less than 2.8 mass% is more preferable, and 0.3 mass% or more and less than 2.8 mass% is still more preferable.
- content of the internal olefin sulfonate in which the sulfonic acid group exists in the 2-position in the C12 and C14 internal olefin sulfonate can be measured by a method such as a nuclear magnetic resonance spectrum. Specifically, it is a numerical value measured by a method using gas chromatography described in Examples described later.
- the mass ratio of the content of the hydroxy compound to the content of the olefin compound (hydroxy compound / olefin compound) in the internal olefin sulfonate having 12 and 14 carbon atoms is light foam quality, instantaneous foaming property, and From the viewpoint of feel after drying, it is preferably 50/50 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0, and 75 / 25 to 100/0 is more preferable, and 75/25 to 95/5 is more preferable.
- the mass ratio of the content of hydroxy and olefin in the internal olefin sulfonate having 12 and 14 carbon atoms of the present invention can be measured by the method described in the examples below.
- the content of the internal olefin sulfonate having 18 or more carbon atoms in the internal olefin sulfonate composition of the present invention is preferably from the viewpoint of light foam quality, instantaneous defoaming property, and feel after drying. It is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less.
- the lower limit of the content of the internal olefin sulfonate having 18 or more carbon atoms is 0% by mass, that is, it is preferable not to contain the internal olefin sulfonate having 18 or more carbon atoms unless it is inevitably mixed.
- the position of the sulfonic acid group is 2 of the olefin chain or the alkane chain from the viewpoint of light foam quality, instantaneous foaming property and feel after drying. It is preferable that the content of the internal olefin sulfonate present in the position is low and the content of the internal olefin sulfonate present in the interior is higher.
- the internal olefin sulfonate composition of the present invention is obtained by sulfonating, neutralizing and hydrolyzing the internal olefin as described above, unreacted raw internal olefin and inorganic compound are contained in the composition. It may remain. It is preferable that the content of these components is small.
- the content of the raw material internal olefin in the internal olefin sulfonate composition of the present invention is based on the amount of internal olefin sulfonate from the viewpoint of light foam quality, instantaneous foaming and feel after drying. It is preferably less than 5.0% by weight, more preferably less than 3.0% by weight, still more preferably less than 1.5% by weight, still more preferably less than 1.0% by weight, and still more preferably less than 0.05% by weight.
- the content of unreacted internal olefin can be measured by the method described in Examples below.
- the content of the inorganic compound in the internal olefin sulfonate composition of the present invention is 7 with respect to the amount of internal olefin sulfonate from the viewpoint of light foam quality, instantaneous foaming and feel after drying. Less than 0.5 mass% is preferable, less than 5.0 mass% is more preferable, less than 3.0 mass% is still more preferable, and less than 1.0 mass% is still more preferable.
- the inorganic compounds include sulfates and alkali agents, and the content of these inorganic compounds can be measured by potentiometric titration. Specifically, it can be measured by the method described in Examples below.
- a hydroxy body and an olefin body having carbon numbers other than the component (A) and the component (B) may be contained.
- the number of carbon atoms of the hydroxy body and olefin body other than the component (A) and the component (B) is preferably 8 to 24 from the viewpoint of light foam quality, instantaneous defoaming property, and feel after drying. 20 is more preferable, 16 to 18 is still more preferable, and 16 is still more preferable.
- These hydroxy bodies and olefin bodies having various carbon numbers are derived from internal olefins used as raw materials.
- the internal olefin sulfonate composition of the present invention may contain, as other components, for example, water serving as a medium, a pH adjuster, a viscosity reducing agent, an organic solvent, and polyhydric alcohols in addition to the above components. .
- the internal olefin sulfonate composition can be produced by sulfonating, neutralizing and hydrolyzing the raw internal olefin composition containing the raw internal olefin having 8 to 24 carbon atoms. More specifically, for example, it can be produced by the method described in Japanese Patent No. 1633184, Japanese Patent No. 2625150, Tenside Surf. Det. 31 (5) 299 (1994) and the like.
- the raw material internal olefin refers to an olefin having a double bond substantially inside the olefin chain as described above.
- the content of the ⁇ -olefin having a double bond in the 1-position in the raw material internal olefin is determined from the viewpoint of light foam quality, instantaneous defoaming property, and feel after drying (A) and (
- the total content of B) is preferably less than 2.8% by mass, and more preferably 2.0% by mass or less.
- the content of the ⁇ -olefin having a double bond in the first position in the raw material internal olefin is 0.01 mass in the total content of the component (A) and the component (B) from the viewpoint of cost and productivity.
- the content of the ⁇ -olefin sulfonate in which the position of the sulfonic acid group is located at the 1-position of the olefin chain or alkane chain is the total content of component (A) and component (B).
- component (A) and component (B) Is more preferably 0.01% by mass or more and less than 2.8% by mass, further preferably 0.1% by mass or more and less than 2.8% by mass, further preferably 0.3% by mass or more and less than 2.8% by mass, 0.3 mass% or more and 2.0 mass% or less are still more preferable.
- the number of carbon atoms in the raw material internal olefin is preferably 8 to 24, more preferably 12 to 20, more preferably 12 to 18 in terms of the light foam quality and instantaneous foaming property of the resulting internal olefin sulfonate composition. Is more preferred, 12 to 16 is still more preferred, 12 to 14 is still more preferred, and 12 and 14 are still more preferred.
- the internal olefin used as a raw material may be used alone or in combination of two or more.
- the content of internal olefin in which the double bond in the raw material internal olefin composition is located at the 2-position Is preferably 15 to 40% by mass, more preferably 15 to 35% by mass.
- the content of the raw material internal olefin having a double bond in the 2-position in the raw material internal olefin composition should be measured by a gas chromatograph (hereinafter abbreviated as GC). Can do. Specifically, it can be measured by the method described in Examples described later.
- GC gas chromatograph
- the raw material internal olefin composition may contain a paraffin component.
- the content of the paraffin component is preferably less than 5% by mass, more preferably less than 3% by mass, further preferably 1% by mass or less, and more preferably 0.1% by mass or less.
- the content of the paraffin component can be measured by, for example, GC-MS.
- the sulfonation reaction can be performed by reacting 1 to 1.2 mol of sulfur trioxide gas with 1 mol of the raw material internal olefin composition.
- the reaction temperature can be 20 to 40 ° C.
- Neutralization is performed by reacting an alkali aqueous solution such as sodium hydroxide, potassium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1 to 1.5 moles with respect to the theoretical value of the sulfonic acid group.
- an alkali aqueous solution such as sodium hydroxide, potassium hydroxide, ammonia, 2-aminoethanol, etc.
- the hydrolysis reaction may be performed at 90 to 200 ° C. for 30 minutes to 3 hours in the presence of water. These reactions can be performed continuously. Moreover, after completion
- the internal olefin sulfonate composition In the production of the internal olefin sulfonate composition, sulfonation, neutralization, and hydrolysis treatments were performed using the raw internal olefin having a distribution of 8 to 24 carbon atoms as the raw internal olefin composition.
- An olefin sulfonate composition may be produced.
- a raw material internal olefin having a single carbon number is used for sulfonation, neutralization and hydrolysis to produce an internal olefin sulfonic acid, and a plurality of types of internal olefin sulfonates having different carbon numbers are prepared.
- the internal olefin sulfonate composition may be produced by mixing.
- the internal olefin sulfonate composition of the present invention is useful as a cleaning component because it exhibits both light foam quality and instantaneous foam breakage at a high level in addition to good foamability. Specifically, it can be used for household cleaners such as hair shampoos, body cleaners, clothing detergents, kitchen detergents and the like, and is particularly useful as a hair shampoo base.
- the cleaning composition of the present invention contains (A) an internal olefin sulfonate having 12 carbon atoms and (B) an internal olefin sulfonate having 14 carbon atoms, like the internal olefin sulfonate composition of the present invention.
- the component mass ratio (A / B) of the component (A) and the component (B) is 10/90 to 90/10, and the component (A) and the component (B) in the internal olefin sulfonate
- the total content of is 60 to 100% by mass.
- other components can be contained. Examples of the other components include other surfactants, foam increasing agents, and auxiliary agents.
- the content of the internal olefin sulfonate in the cleaning composition is preferably 0.1 to 80% by mass, more preferably 1 to 50% by mass, and still more preferably 2 to 30% by mass.
- alkyl sulfates and alkyl polyoxyalkylene sulfates are preferable.
- the adjuvant is not particularly limited.
- the cleaning composition of the present invention can be produced, for example, by blending the internal olefin sulfonate composition obtained as described above, and may be produced by further mixing the above components.
- the present invention further discloses the following internal olefin composition and detergent composition.
- the mass ratio (A / B) of component (A) to component (B) in the internal olefin sulfonate composition is preferably 25/75 to 90/10, more preferably 50/50 to The internal olefin sulfonate composition according to ⁇ 1>, which is 90/10, more preferably 75/25 to 90/10, and still more preferably 80/20 to 90/10.
- the mass ratio (A / B) of component (A) to component (B) in the internal olefin sulfonate composition is preferably 10/90 to 80/20, more preferably 10/90 to The internal olefin sulfonate composition according to ⁇ 1>, which is 70/30, more preferably 10/90 to 30/70, and further preferably 10/90 to 20/80.
- the lower limit of the total content of the component (A) and the component (B) in the internal olefin sulfonate composition is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably.
- Internal olefin sulfonate composition The content of the internal olefin sulfonate having a sulfonic acid group at the 2-position in the internal olefin sulfonate having 12 and 14 carbon atoms is preferably 28% by mass or less, more preferably 25% by mass. Less than, more preferably 23% by mass or less, still more preferably 22% by mass or less, preferably 5% by mass or more, more preferably 7% by mass or more, and preferably 15% by mass or more.
- the mass ratio of the content of hydroxy body to the content of olefin body of the internal olefin sulfonate having 12 and 14 carbon atoms is preferably 50/50 to 100/0. More preferably 60/40 to 100/0, still more preferably 70/30 to 100/0, still more preferably 75/25 to 100/0, and still more preferably 75/25 to 95/5.
- the internal olefin sulfonate composition according to any one of ⁇ 1> to ⁇ 5>.
- the content of the internal olefin sulfonate having 18 or more carbon atoms is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and the lower limit is The internal olefin sulfonate composition according to any one of ⁇ 1> to ⁇ 6>, which is preferably 0% by mass.
- the content of the raw material internal olefin in the internal olefin sulfonate composition is preferably less than 5.0 mass%, more preferably less than 3.0 mass% with respect to the internal olefin sulfonate content.
- the content of the inorganic compound in the internal olefin sulfonate composition is preferably less than 7.5% by mass and more preferably less than 5.0% by mass with respect to the amount of the internal olefin sulfonate. Yes, more preferably less than 3.0% by weight, even more preferably less than 1.0% by weight, ⁇ 1> to ⁇ 8> any one of the internal olefin sulfonate compositions.
- the carbon number of the hydroxy body and olefin body other than the component (A) and the component (B) in the internal olefin sulfonate composition is preferably 8 to 24, more preferably 16
- the raw material internal olefin composition containing the raw material internal olefin and the content of the raw material internal olefin having a double bond at the 2-position is preferably 15 to 40% by mass
- the internal olefin sulfonate composition according to ⁇ 11>, wherein the content of the raw internal olefin having a double bond in the 2-position in the raw internal olefin composition is more preferably 15 to 35% by mass.
- a cleaning composition comprising the internal olefin sulfonate composition according to any one of ⁇ 1> to ⁇ 12>.
- ⁇ 14> containing (A) an internal olefin sulfonate having 12 carbon atoms and (B) an internal olefin sulfonate having 14 carbon atoms, and the mass ratio (A / B) of the component (A) and the component (B). ) Is 10/90 to 90/10, and the total content of the component (A) and the component (B) is 60 to 100% by mass.
- ⁇ 15> The cleaning composition according to ⁇ 13> or ⁇ 14>, wherein the content of the internal olefin sulfonate is preferably 0.1 to 80% by mass.
- ⁇ 16> The cleaning composition according to any one of ⁇ 13> to ⁇ 15>, preferably containing one or more selected from alkyl sulfates and alkyl polyoxyalkylene sulfates.
- ⁇ 17> A method for washing hair, wherein the cleaning composition according to any one of ⁇ 13> to ⁇ 16> is applied to the hair and then rinsed.
- ⁇ 18> A method for washing the skin after applying the cleaning composition according to any one of ⁇ 13> to ⁇ 16> to the skin.
- ⁇ 19> Use of any one of the cleaning compositions of ⁇ 13> to ⁇ 16> for washing hair.
- ⁇ 20> Use of any one of the cleaning compositions of ⁇ 13> to ⁇ 16> for cleaning the skin.
- Measurement conditions (i) Method of measuring double bond position of internal olefin The double bond position of internal olefin was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, dimethyl disulfide was reacted with an internal olefin to obtain a dithiolated derivative, and then each component was separated by GC. The double bond position of the internal olefin was determined from each peak area.
- GC gas chromatography
- GC device “HP6890, HEWLETT” manufactured by PACKARD
- column “Ultra-Alloy-1HT capillary column” (30 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m, manufactured by Frontier Laboratories), detector (hydrogen flame ion detector (FID)) ), Injection temperature 300 ° C., detector temperature 350 ° C., He flow rate 4.6 mL / min.
- GC device “Agilent Technology 6850” (manufactured by Agilent Technologies), column “HP-1 capillary column” (30 m ⁇ 320 ⁇ m ⁇ 0.25 ⁇ m, manufactured by Agilent Technologies), detector (hydrogen flame ion detector (FID)), injection Temperature 300 ° C., detector temperature 300 ° C., He flow rate 1.0 mL / min. , Oven (60 ° C. (0 min.) ⁇ 10 ° C./min. ⁇ 300° C. (10 min.).
- MS apparatus “Agilent Technology 1100MS SL (G1946D))” (manufactured by Agilent Technologies), MS Detection (negative ion detection m / z 60-1600, UV 240n m)
- GC device “Agilent Technology 6850” (manufactured by Agilent Technologies), column “Ultra-Alloy-1HT capillary column 15 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m” (manufactured by Frontier Laboratories), detector (hydrogen ion detector (FID)) ), Injection temperature 300 ° C., detector temperature 350 ° C., He flow rate 3.8 mL / min.
- (V) Measuring method of content of inorganic compound The content of the inorganic compound was measured by potentiometric titration or neutralization titration. Specifically, the content of Na 2 SO 4 was quantified by determining the sulfate radical (SO 4 2 ⁇ ) by potentiometric titration. The content of NaOH was quantified by neutralization titration with dilute hydrochloric acid.
- (Vi) Measuring method of content of paraffin component The content of the paraffin component was measured by GC. Specifically, ethanol and petroleum ether were added to the internal olefin sulfonate aqueous solution, followed by extraction to obtain paraffin in the petroleum ether phase. The amount of paraffin was quantified from the GC peak area. In addition, the apparatus and analysis conditions used for the measurement are the same as the measurement of the content of the raw material internal olefin.
- the crude internal olefin was transferred to a distillation flask and distilled at 124-136 ° C./7.5 mmHg to obtain an internal olefin having a carbon number of 12 and an olefin purity of 100%.
- the crude internal olefin was transferred to a distillation flask and distilled at 124-136 ° C./7.5 mmHg to obtain an internal olefin having a carbon number of 14% with an olefin purity of 100.
- Double bond distribution of the obtained internal olefin Is a total of 1.3 mass% at C1, 31.8 mass% at C2, 23.8 mass% at C3, 21.0 mass% at C4, 8.6 mass% at C5, C6, and 7th. It was 13.6% by mass.
- the obtained sulfonated product was added to an alkaline aqueous solution prepared with 1.5 mol times the amount of sodium hydroxide with respect to the theoretical acid value, and neutralized at 30 ° C. for 1 hour with stirring.
- the neutralized product was hydrolyzed by heating at 160 ° C. for 1 hour in an autoclave to obtain a crude product of C12 internal sodium olefin sulfonate. 300 g of the crude product was transferred to a separatory funnel, 300 mL of ethanol was added, and 300 mL of petroleum ether was added at one time to extract and remove oil-soluble impurities.
- the inorganic compound (main component was sodium sulfate) precipitated at the oil / water interface by addition of ethanol was also separated and removed from the water phase by the oil / water separation operation. This extraction and removal operation was performed three times.
- the C12 internal olefin sulfonic acid sodium salt was obtained by evaporating the water phase side to dryness.
- the mass ratio of hydroxy body (sodium hydroxyalkanesulfonate) / olefin body (sodium olefinsulfonate) in the obtained internal sodium olefinsulfonate was 92/8.
- content of the raw material internal olefin contained in the obtained internal olefin sodium sulfonate was less than 100 ppm (less than GC detection lower limit), and the inorganic compound was 0.2 mass%. Furthermore, the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position was 21.0% by mass.
- Table 3 shows the evaluation results for alkyl polyoxyethylene sulfate (AES), ⁇ -olefin sulfonate (AOS) and secondary alkyl sulfonate (SAS). The concentration of these surfactants in the cleaning composition was adjusted to 13% by mass.
- AES alkyl polyoxyethylene sulfate
- AOS ⁇ -olefin sulfonate
- SAS secondary alkyl sulfonate
- the internal olefin sulfonate composition of the present invention can exhibit good foaming properties, light foam quality, and instantaneous foaming properties at a high level, it can be used for hair shampoos, body washing agents, and clothing. It can be suitably used in the field of household detergents such as detergents, kitchen detergents and residential detergents, and is also suitable for cosmetic emulsifiers, industrial emulsifiers, industrial detergents and the like.
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Abstract
Description
こうして得られる内部オレフィンスルホン酸塩は、生分解性等が良好であることが知られているが、起泡性、泡質をはじめとする洗浄剤としての基本性能に関しては、アルキルポリオキシアルキレン硫酸エステル塩等の汎用界面活性剤と比較して未だ十分とはいえず、更なる向上が望まれている。更に、近年の節水に対する意識の高まりや、消費者嗜好の多様化により、衣料用洗剤、食器用洗剤、シャンプー等の主活性剤に用いる場合には、良好な起泡性に加えて、軽やかな泡質や瞬間的な泡切れ性という新たな付加価値も求められている。具体的には、洗浄時には気泡が大きく、かつ気泡密度及び泡粘度が低いことにより、軽やかな泡質をもたらして速やかに泡を行き渡せることを可能とするとともに、すすぎ時には瞬時に消泡する瞬間的な泡切れ性を有することにより、快適な洗浄と短時間でのすすぎを容易にする界面活性剤組成物の開発が望まれている。このような付加価値は、例えば毛髪用シャンプーや身体洗浄料において有用である。すなわち、起床後外出前や就寝前の限られた時間内に毛髪や体を洗う習慣のある人が増えつつあるが、泡を毛髪全体に行き渡らせたり、毛髪のすみずみまで十分に濯いだりするのにとかく時間を要する傾向にある。これらは、泡質が微細で泡の粘性が高いことに由来するところが大きい。そのため、軽やかな泡質と瞬間的な泡切れ性を有する界面活性剤組成物をシャンプーに配合することができれば、短時間のうちに十分に洗浄することが可能となり、快適な洗浄が可能となるだけでなく乾燥後のすっきりした感触をもたらすことも可能となり、節水の実現にも繋がる。
(特許文献2)特開昭61-134366号公報
(特許文献3)特開昭60-32759号公報
(特許文献4)特開2003-81935号公報
(特許文献5)米国特許第5078916号明細書
(特許文献6)国際公開第2010/129051号
したがって、本発明は、良好な起泡性、軽やかな泡質及び瞬間的な泡切れ性を十分に高めることができる内部オレフィンスルホン酸塩組成物、及び内部オレフィンスルホン酸塩を含有する洗浄剤組成物に関する。
<内部オレフィンスルホン酸塩組成物>
本発明の内部オレフィンスルホン酸塩組成物は、(A)炭素数12の内部オレフィンスルホン酸塩及び(B)炭素数14の内部オレフィンスルホン酸塩を含有し、当該成分(A)と成分(B)の含有質量比(A/B)が10/90~90/10であり、かつ当該成分(A)及び成分(B)の合計含有量が60~100質量%である。
成分(A)及び成分(B)におけるスルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量は、これらの観点を総合すると、成分(A)及び成分(B)の合計含有量中に、5質量%以上28質量%が好ましく、7質量%以上28質量%未満がより好ましく、7質量%以上25質量%未満が更に好ましく、15質量%以上23質量%以下が更に好ましく、19質量%以上22質量%以下が更に好ましい。
また、軽やかな泡質、瞬間的な泡切れ性、及び乾燥後の感触の点から、炭素数18以上の内部オレフィンスルホン酸塩においても、当該スルホン酸基の位置がオレフィン鎖又はアルカン鎖の2位に存在する内部オレフィンスルホン酸塩の含有量が低く、より内部に存在する内部オレフィンスルホン酸塩の含有量が高いのが好ましい。
本発明の内部オレフィンスルホン酸塩組成物中における原料内部オレフィンの含有量は、軽やかな泡質、瞬間的な泡切れ性、及び乾燥後の感触の点から、内部オレフィンスルホン酸塩量に対して5.0質量%未満が好ましく、3.0質量%未満がより好ましく、1.5質量%未満が更に好ましく、1.0質量%未満が更に好ましく、0.05質量%未満がより更に好ましい。
内部オレフィンスルホン酸塩組成物は、炭素数8~24の原料内部オレフィンを含有する原料内部オレフィン組成物をスルホン化し、中和し、加水分解して製造することができる。より具体的には、例えば、特許第1633184号公報、特許第2625150号公報、Tenside Surf.Det.31(5)299(1994)等に記載の方法により製造することができる。
原料内部オレフィンの炭素数は、得られる内部オレフィンスルホン酸塩組成物の軽やかな泡質、及び瞬間的な泡切れ性の点から、8~24が好ましく、12~20がより好ましく、12~18がより好ましく、12~16が更に好ましく、12~14が更に好ましく、12及び14が更に好ましい。原料として使用される内部オレフィンは、1種単独でもよいし、2種以上を併用してもよい。
本発明の洗浄剤組成物は、前記本発明の内部オレフィンスルホン酸塩組成物と同様、(A)炭素数12の内部オレフィンスルホン酸塩及び(B)炭素数14の内部オレフィンスルホン酸塩を含有し、当該成分(A)と成分(B)の含有質量比(A/B)が10/90~90/10であり、かつ内部オレフィンスルホン酸塩中の当該成分(A)及び成分(B)の合計含有量が60~100質量%であること以外は特に制限はない。目的に応じて、その他の成分を含有することができる。前記その他の成分としては、他の界面活性剤、増泡剤、補助剤などが挙げられる。洗浄剤組成物中の内部オレフィンスルホン酸塩の含有量は、0.1~80質量%が好ましく、1~50質量%がより好ましく、2~30質量%が更に好ましい。
<3>内部オレフィンスルホン酸塩組成物における成分(A)と成分(B)の含有質量比(A/B)が、好ましくは10/90~80/20であり、より好ましくは10/90~70/30であり、更に好ましくは10/90~30/70であり、更に好ましくは10/90~20/80である<1>の内部オレフィンスルホン酸塩組成物。
<4>内部オレフィンスルホン酸塩組成物中の成分(A)と成分(B)の合計含有量の下限が、好ましくは70質量%以上であり、より好ましくは80質量%以上であり、更に好ましくは90質量%以上であり、更に好ましくは95質量%以上であり、更に好ましくは96.5質量%以上であり、更に好ましくは97質量%以上である<1>~<3>いずれか1の内部オレフィンスルホン酸塩組成物。
<5>炭素数12及び14の内部オレフィンスルホン酸塩の、スルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量が、好ましくは28質量%以下であり、より好ましくは25質量%未満であり、更に好ましくは23質量%以下であり、更に好ましくは22質量%以下であり、好ましくは5質量%以上であり、より好ましくは7質量%以上であり、好ましくは15質量%以上であり、更に好ましくは19質量%以上である<1>~<4>いずれか1の内部オレフィンスルホン酸塩組成物。
<6>炭素数12及び14の内部オレフィンスルホン酸塩の、ヒドロキシ体の含有量とオレフィン体の含有量の質量比(ヒドロキシ体/オレフィン体)は、好ましくは50/50~100/0であり、より好ましくは60/40~100/0であり、更に好ましくは70/30~100/0であり、更に好ましくは75/25~100/0であり、更に好ましくは75/25~95/5である<1>~<5>いずれか1の内部オレフィンスルホン酸塩組成物。
<7>炭素数18以上の内部オレフィンスルホン酸塩の含有量が、好ましくは3質量%以下であり、より好ましくは2質量%以下であり、更に好ましくは1質量%以下であり、その下限は好ましくは0質量%である<1>~<6>いずれか1の内部オレフィンスルホン酸塩組成物。
<8>内部オレフィンスルホン酸塩組成物中における原料内部オレフィンの含有量が、内部オレフィンスルホン酸塩量に対して好ましくは5.0質量%未満であり、より好ましくは3.0質量%未満であり、更に好ましくは1.5質量%未満であり、更に好ましくは1.0質量%未満であり、より更に好ましくは0.05質量%未満である<1>~<7>いずれか1の内部オレフィンスルホン酸塩組成物。
<9>内部オレフィンスルホン酸塩組成物中における無機化合物の含有量が、内部オレフィンスルホン酸塩量に対して、好ましくは7.5質量%未満であり、より好ましくは5.0質量%未満であり、更に好ましくは3.0質量%未満であり、より更に好ましくは1.0質量%未満である<1>~<8>いずれか1の内部オレフィンスルホン酸塩組成物。
<10>内部オレフィンスルホン酸塩組成物中の前記成分(A)及び成分(B)以外の炭素数を有するヒドロキシ体及びオレフィン体の炭素数が、好ましくは8~24であり、より好ましくは16~20であり、更に好ましくは16~18であり、更に好ましくは16である<1>~<9>いずれか1の内部オレフィンスルホン酸塩組成物。
<11>原料内部オレフィンを含有し、かつ二重結合が2位に存在する原料内部オレフィンの含有量が、好ましくは15~40質量%である原料内部オレフィン組成物をスルホン化処理した後、中和し、次いで加水分解処理することにより得られる<1>~<10>いずれか1の内部オレフィンスルホン酸塩組成物。
<12>原料内部オレフィン組成物における二重結合が2位に存在する原料内部オレフィンの含有量が、より好ましくは15~35質量%である<11>の内部オレフィンスルホン酸塩組成物。
<13><1>~<12>いずれか1の内部オレフィンスルホン酸塩組成物を配合してなる洗浄剤組成物。
<14>(A)炭素数12の内部オレフィンスルホン酸塩及び(B)炭素数14の内部オレフィンスルホン酸塩を含有し、当該成分(A)と成分(B)の含有質量比(A/B)が10/90~90/10であり、かつ当該成分(A)及び成分(B)の合計含有量が60~100質量%である洗浄剤組成物。
<15>内部オレフィンスルホン酸塩の含有量が、好ましくは0.1~80質量%である<13>又は<14>の洗浄剤組成物。
<16>好ましくはアルキル硫酸塩及びアルキルポリオキシアルキレン硫酸塩から選ばれる1種以上を含有する<13>~<15>いずれか1の洗浄剤組成物。
<17><13>~<16>いずれか1の洗浄剤組成物を毛髪に適用して洗浄した後、すすぐ、毛髪の洗浄方法。
<18><13>~<16>いずれか1の洗浄剤組成物を皮膚に適用した後、すすぐ、皮膚の洗浄方法。
<19><13>~<16>いずれか1の洗浄剤組成物の、毛髪を洗浄するための使用。
<20><13>~<16>いずれか1の洗浄剤組成物の、皮膚を洗浄するための使用。
(i)内部オレフィンの二重結合位置の測定方法
内部オレフィンの二重結合位置は、ガスクロマトグラフィー(以下、GCと省略)により測定した。具体的には、内部オレフィンに対しジメチルジスルフィドを反応させることでジチオ化誘導体とした後、各成分をGCで分離した。それぞれのピーク面積より内部オレフィンの二重結合位置を求めた。
尚、測定に使用した装置および分析条件は次の通りである。GC装置「HP6890,HEWLETT」(PACKARD社製)、カラム「Ultra-Alloy-1HTキャピラリーカラム」(30m×250μm×0.15μm、フロンティア・ラボ株式会社製)、検出器(水素炎イオン検出器(FID))、インジェクション温度300℃、ディテクター温度350℃、He流量4.6mL/min.
スルホン酸基の結合位置は、GCにより測定した。具体的には、内部オレフィンスルホン酸塩に対しトリメチルシリルジアゾメタンを反応させることでメチルエステル化誘導体とした後、各成分をGCで分離した。それぞれのピーク面積比を質量比として、スルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量を算出した。
尚、測定に使用した装置および分析条件は次の通りである。GC装置「アジレントテクノロジー6850」(アジレントテクノロジー社製)、カラム「HP-1キャピラリーカラム」(30m×320μm×0.25μm,アジレントテクノロジー社製)、検出器(水素炎イオン検出器(FID))、インジェクション温度300℃、ディテクター温度300℃、He流量1.0mL/min.、オーブン(60℃(0min.)→10℃/min.→300℃(10min.)。
ヒドロキシ体/オレフィン体の質量比は、HPLC-MSにより測定した。具体的には、HPLCによりヒドロキシ体とオレフィン体を分離し、それぞれをMSにかけることで同定した。そのGC-MSピーク面積から各々の割合を求めた。
尚、測定に使用した装置および条件は次の通りである。HPLC装置「アジレントテクノロジー1100」(アジレントテクノロジー社製)、カラム「L-columnODS4.6×150mm」(一般財団法人化学物質評価研究機構製)、サンプル調製(メタノールで1000倍希釈)、溶離液A(10mM酢酸アンモニウム添加水)、溶離液B(10mM酢酸アンモニウム添加メタノール)、グラジェント(0min.(A/B=30/70%)→10min.(30/70%)→55min.(0/100%)→65min.(0/100%)→66min.(30/70%)→75min.(30/70%))、MS装置「アジレントテクノロジー1100MS SL(G1946D))」(アジレントテクノロジー社製),MS検出(陰イオン検出 m/z60-1600、UV240nm)
原料内部オレフィンの含有量は、GCにより測定した。具体的には、内部オレフィンスルホン酸塩水溶液にエタノールと石油エーテルを添加した後、抽出し石油エーテル相にオレフィンを得た。そのGCピーク面積からオレフィン量を定量した。
尚、測定に使用した装置および分析条件は次の通りである。GC装置「アジレントテクノロジー6850」(アジレントテクノロジー社製)、カラム「Ultra-Alloy-1HTキャピラリーカラム15m×250μm×0.15μm」(フロンティア・ラボ株式会社製)、検出器(水素炎イオン検出器(FID))、インジェクション温度300℃、ディテクター温度350℃、He流量3.8mL/min.
無機化合物の含有量は、電位差滴定や中和滴定により測定した。具体的には、Na2SO4の含有量は、硫酸根(SO4 2-)を電位差滴定によって求めることで定量した。また、NaOHの含有量は、希塩酸で中和滴定することで定量した。
パラフィン成分の含有量は、GCにより測定した。具体的には、内部オレフィンスルホン酸塩水溶液にエタノールと石油エーテルを添加した後、抽出し、石油エーテル相にパラフィンを得た。そのGCピーク面積からパラフィン量を定量した。
なお、測定に使用した装置および分析条件は原料内部オレフィンの含有量の測定と同様である。
[製造例A] 炭素数12、2重結合2位33.1質量%の内部オレフィンの合成
攪拌装置付きフラスコに1-ドデセン「リニアレン12、出光興産株式会社製」(6000g(35.6モル)、固体酸触媒としてプロトン性β―ゼオライト(CP-814E、Zeolyst社)180g(原料α―オレフィンに対して3質量%)を仕込み、攪拌下、120℃にて20時間、反応を行った。続いて、粗内部オレフィンを蒸留用フラスコに移し、124-136℃/7.5mmHgで蒸留することでオレフィン純度100%の炭素数12の内部オレフィンを得た。得られた内部オレフィンの二重結合分布は、C1位0.5質量%、C2位33.1質量%、C3位質量23.7質量%、C4位21.2質量%、C5位15.0質量%、C6位6.6質量%であった。
攪拌装置付きフラスコに1-テトラデセン「リニアレン14、出光興産株式会社製」(6000g(30.6モル)、固体酸触媒としてプロトン性β-ゼオライト(CP-814E、Zeolyst社)180g(原料α-オレフィンに対して3質量%)を仕込み、攪拌下、120℃にて20時間、反応を行った。続いて、粗内部オレフィンを蒸留用フラスコに移し、124-136℃/7.5mmHgで蒸留することでオレフィン純度100%の炭素数14の内部オレフィンを得た。得られた内部オレフィンの二重結合分布は、C1位1.3質量%、C2位31.8質量%、C3位23.8質量%、C4位21.0質量%、C5位8.6質量%、C6、7位の合計が13.6質量%であった。
[製造例1] (C12内部オレフィンスルホン酸塩の合成)
製造例Aで得た炭素数12の内部オレフィン(二重結合が2位に存在する内部オレフィンの含有量が33.1質量%)を、外部にジャケットを有する薄膜式スルホン化反応器に入れ、反応器外部ジャケットに20℃の冷却水を通液する条件下で三酸化硫黄ガスを用いてスルホン化反応を行った。スルホン化反応の際のSO3/内部オレフィンのモル比は1.09に設定した。得られたスルホン化物を、理論酸価に対し1.5モル倍量の水酸化ナトリウムで調製したアルカリ水溶液へ添加し、攪拌しながら30℃、1時間中和した。中和物をオートクレーブ中で160℃、1時間加熱することで加水分解を行い、C12内部オレフィンスルホン酸ナトリウム粗生成物を得た。該粗生成物300gを分液漏斗に移し、エタノール300mLを加えた後、1回あたり石油エーテル300mLを加えて油溶性の不純物を抽出除去した。この際、エタノールの添加により油水界面に析出した無機化合物(主成分は芒硝)も、油水分離操作により水相から分離除去した。この抽出除去操作を3回おこなった。水相側を蒸発乾固することで、C12内部オレフィンスルホン酸ナトリウムを得た。得られた内部オレフィンスルホン酸ナトリウム中のヒドロキシ体(ヒドロキシアルカンスルホン酸ナトリウム)/オレフィン体(オレフィンスルホン酸ナトリウム)の質量比は92/8であった。また、得られた内部オレフィンスルホン酸ナトリウム中に含有される原料内部オレフィンの含有量は100ppm未満(GC検出下限未満)、無機化合物は0.2質量%であった。さらに、スルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量は21.0質量%であった。
製造例Bで得た炭素数14の内部オレフィン(二重結合が2位に存在する内部オレフィンの含有量が31.8質量%)から、製造例1と同様の条件でC14内部オレフィンスルホン酸ナトリウムを得た。
得られた内部オレフィンスルホン酸ナトリウム中のヒドロキシ体/オレフィン体の質量比率は93/7であった。また、得られた内部オレフィンスルホン酸ナトリウム中の原料内部オレフィンの含有量は100ppm未満(GC検出下限未満)、無機化合物は0質量%であった。さらに、スルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量は21.7質量%であった。
製造例1で得られた組成物と製造例2で得られた組成物を、質量比10:90で配合及び混合して、内部オレフィンスルホン酸塩組成物1を得た。
製造例1で得られた組成物と製造例2で得られた組成物を質量比25:75で配合及び混合して、内部オレフィンスルホン酸塩組成物2を得た。
製造例1で得られた組成物と製造例2で得られた組成物を質量比50:50で配合及び混合して、内部オレフィンスルホン酸塩組成物3を得た。
製造例1で得られた組成物と製造例2で得られた組成物を質量比75:25で配合及び混合して、内部オレフィンスルホン酸塩組成物4を得た。
製造例1で得られた組成物と製造例2で得られた組成物を質量比90:10で配合及び混合して、内部オレフィンスルホン酸塩組成物5を得た。
表1に示すプレーンシャンプーで毛束(ブリーチ、ヘアカラーなどの処理をしていない日本人毛、約20cm、15g)を洗浄後、表2に示すプレーンリンスを塗布した後、水道水ですすぎ、評価用トレスを得た。
製造例3~7で得た内部オレフィンスルホン酸塩組成物1~5をイオン交換水に溶解することにより調製した内部オレフィンスルホン酸塩組成物の13質量%水溶液を用い、5人の専門パネラーが、以下に示す評価基準、評価方法により、起泡性、泡質の軽やかさ、すすぎ時の泡切れ性、及び洗浄後にタオルで拭き取って乾燥した際における感触(残留感の無さ)の評価を行った。(具体的には、表3に示す洗浄剤組成物1.0gを評価用トレスに取り、泡立て、洗浄、すすぎの操作を行った。)結果を表3に示す。
なお、表3には、アルキルポリオキシエチレン硫酸塩(AES)、α-オレフィンスルホン酸塩(AOS)及び第二級アルキルスルホン酸塩(SAS)についての評価結果も示した。これらの界面活性剤の洗浄剤組成物中における濃度を13質量%に調製した。
各成分をビーカーに取り、80℃に加温後、混合し、均一に溶解したことを確認した後、冷却して、プレーンシャンプーを得た。
塩化オクタデシロキシプロピルトリメチルアンモニウム及びステアリルアルコールをビーカー(A)に入れ、80℃に加温して融解させた。別のビーカー(B)に精製水およびメチルパラベンをビーカーに取り、攪拌しながら80℃に加温し、均一に溶解したことを確認した。その後、ビーカー(B)を80℃で攪拌しながら、ビーカー(A)中の混合液を加え、30分乳化を行い、加熱を中止し、室温まで冷却して、プレーンリンスを得た。
・起泡性
5:起泡性が非常に良い
4:起泡性が良い
3:普通の起泡性(参考比較例3:SASと同等)
2:起泡性が悪い
1:起泡性が非常に悪く洗えない
・泡質の軽やかさ
5:泡質が非常に軽く、気泡が大きく、洗いやすい
4:泡質がやや軽く良い
3:泡質が普通(参考比較例1:AESと同等)
2:泡質がやや重く、悪い
1:泡質が非常に重く、洗いにくい
・すすぎ時における泡切れ性
5:すすいだ瞬間に泡切れが起こり(消泡)、すすぎやすい
4:泡切れがすばやい
3:普通(参考比較例2:AOSと同等)
2:泡切れが遅い
1:泡切れが非常に遅く、すすぎにくい
・洗浄後にタオルで拭き取って乾燥した後の感触
5:洗浄剤の残留感がなく、非常にすっきりとした洗いあがり
4:ややすっきりとした洗いあがり
3:普通(参考比較例1:AESと同等)
2:やや洗浄剤の残留感があり、あまりすっきりとしない洗いあがり
1:洗浄剤の残留感が強く、全くすっきりしない洗いあがり
製造例3~7で得た内部オレフィンスルホン酸塩組成物1~5をイオン交換水に溶解することにより調製した内部オレフィンスルホン酸塩組成物の13質量%水溶液を用い、5人のパネラーが手洗いを行い、以下に示す評価基準、評価方法により、起泡性、すすぎ時の泡切れ、及び洗浄後にタオルで拭き取って乾燥した際における感触(残留感の無さ)の評価を行った。具体的には、表3に示す内部オレフィンスルホン酸塩組成物を用いて調製した13質量%水溶液1.0gを手に取り、泡立て、洗浄した後、すすぎ、その後にタオルで拭き取って乾燥した。結果を表3に示す。
・起泡性
5:起泡性が非常に良い
4:起泡性が良い
3:普通の起泡性(参考比較例3:SASと同等)
2:起泡性が悪い
1:起泡性が非常に悪く洗えない
・すすぎ時における泡切れ性
5:すすいだ瞬間に泡切れが起こり(消泡)、すすぎやすい
4:泡切れがすばやい
3:普通(参考比較例2:AOSと同等)
2:泡切れが遅い
1:泡切れが非常に遅く、すすぎにくい
・洗浄後にタオルで拭き取って乾燥した後の感触
5:洗浄剤の残留感がなく、非常にすっきりとした洗いあがり
4:ややすっきりとした洗いあがり
3:普通(参考比較例2:AOSと同等)
2:やや洗浄剤の残留感があり、あまりすっきりとしない洗いあがり
1:洗浄剤の残留感が強く、全くすっきりしない洗いあがり
Claims (12)
- (A)炭素数12の内部オレフィンスルホン酸塩及び(B)炭素数14の内部オレフィンスルホン酸塩を含有し、当該成分(A)と成分(B)の含有質量比(A/B)が10/90~90/10であり、かつ内部オレフィンスルホン酸塩組成物中の当該成分(A)及び成分(B)の合計含有量が60~100質量%である内部オレフィンスルホン酸塩組成物。
- 炭素数12及び炭素数14の内部オレフィンスルホン酸塩におけるスルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量が、28質量%以下である請求項1記載の内部オレフィンスルホン酸塩組成物。
- 炭素数12及び炭素数14の内部オレフィンスルホン酸塩におけるヒドロキシ体の含有量と炭素数12及び炭素数14の内部オレフィンスルホン酸塩のオレフィン体の含有量の質量比(ヒドロキシ体/オレフィン体)が、50/50~100/0である請求項1又は2記載の内部オレフィンスルホン酸塩組成物。
- 内部オレフィンスルホン酸塩組成物中の原料内部オレフィンの含有量が、内部オレフィンスルホン酸塩量に対して1.5質量%未満である請求項1~3のいずれか1項に記載の内部オレフィンスルホン酸塩組成物。
- 内部オレフィンスルホン酸塩組成物中の無機化合物の含有量が、内部オレフィンスルホン酸塩量に対して7.5質量%未満である請求項1~4のいずれか1項に記載の内部オレフィンスルホン酸塩組成物。
- 原料内部オレフィンを含有し、かつ二重結合が2位に存在する原料内部オレフィンの含有量が15~40質量%である原料内部オレフィン組成物をスルホン化処理した後、中和し、次いで加水分解処理することにより得られる請求項1~5のいずれか1項に記載の内部オレフィンスルホン酸塩組成物。
- 内部オレフィンスルホン酸塩組成物における成分(A)と成分(B)の含有質量比(A/B)が80/20~90/10である請求項1~6のいずれか1項に記載の内部オレフィンスルホン酸塩組成物。
- 内部オレフィンスルホン酸塩組成物における成分(A)と成分(B)の含有質量比(A/B)が10/90~20/80である請求項1~6のいずれか1項に記載の内部オレフィンスルホン酸塩組成物。
- 請求項1~8のいずれかに記載の内部オレフィンスルホン酸塩組成物を配合してなる洗浄剤組成物。
- (A)炭素数12の内部オレフィンスルホン酸塩及び(B)炭素数14の内部オレフィンスルホン酸塩を含有し、当該成分(A)と成分(B)の含有質量比(A/B)が10/90~90/10であり、かつ内部オレフィンスルホン酸塩中の当該成分(A)及び成分(B)の合計含有量が60~100質量%である洗浄剤組成物。
- (A)炭素数16の内部オレフィンスルホン酸塩と(B)炭素数14の内部オレフィンスルホン酸塩の合計含有量が、0.1~80質量%である請求項9又は10記載の洗浄剤組成物。
- アルキル硫酸塩及びアルキルポリオキシアルキレン硫酸塩から選ばれる1種以上を含有する請求項9~11のいずれか1項に記載の洗浄剤組成物。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014177620A (ja) * | 2013-02-13 | 2014-09-25 | Kao Corp | 内部オレフィンスルホン酸塩組成物 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016147928A (ja) * | 2015-02-10 | 2016-08-18 | 花王株式会社 | 手洗い用食器洗浄剤組成物 |
US20180371360A1 (en) * | 2015-12-10 | 2018-12-27 | Kao Corporation | Surfactant composition |
WO2017098638A1 (ja) * | 2015-12-10 | 2017-06-15 | 花王株式会社 | 界面活性剤組成物 |
BR112018011701A2 (ja) * | 2015-12-10 | 2018-12-04 | Kao Corporation | Surface-active agent constituent |
CN109196081B (zh) | 2016-05-31 | 2021-05-11 | 花王株式会社 | 纤维制品用清洁剂组合物 |
RU2737429C2 (ru) | 2016-05-31 | 2020-11-30 | Као Корпорейшн | Жидкая детергентная композиция для текстильных продуктов |
JP6670178B2 (ja) * | 2016-05-31 | 2020-03-18 | 花王株式会社 | 繊維製品の洗濯方法 |
WO2017209120A1 (ja) | 2016-05-31 | 2017-12-07 | 花王株式会社 | 繊維製品用液体洗浄剤組成物 |
AU2017342590A1 (en) * | 2016-10-14 | 2019-04-04 | Kao Corporation | Fiber product finishing agent composition |
JP6482050B1 (ja) * | 2017-07-14 | 2019-03-13 | 花王株式会社 | 硬質物品の洗浄方法 |
WO2023248162A1 (en) | 2022-06-24 | 2023-12-28 | Johnson & Johnson Consumer Inc. | Sustainable shampoo |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58157758A (ja) * | 1982-03-15 | 1983-09-19 | Lion Corp | 高濃度オレフインスルホン酸塩溶液の製造法 |
JPS59222466A (ja) * | 1983-05-31 | 1984-12-14 | Lion Corp | オレフインのスルホン化方法 |
JPS6032759A (ja) | 1983-07-29 | 1985-02-19 | Lion Corp | 内部オレフインスルホン酸塩の製造方法 |
JPS61134366A (ja) | 1984-12-06 | 1986-06-21 | Lion Corp | 界面活性剤中の油分分離方法 |
JPH0257598B2 (ja) | 1982-08-10 | 1990-12-05 | Lion Corp | |
JPH03126795A (ja) * | 1989-10-11 | 1991-05-29 | Lion Corp | 高濃度オレフィンスルホン酸塩水性スラリーの製造方法 |
JPH03126793A (ja) * | 1989-10-06 | 1991-05-29 | Unilever Nv | 洗剤組成物 |
US5078916A (en) | 1989-01-03 | 1992-01-07 | Shell Oil Company | Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds |
JP2625150B2 (ja) | 1988-04-21 | 1997-07-02 | ライオン株式会社 | インナーオレフィンスルホネートの製法 |
JP2003081935A (ja) | 2001-09-10 | 2003-03-19 | Lion Corp | 内部オレフィンスルホン酸塩及びそれを含む洗浄剤組成物 |
WO2010129051A1 (en) | 2009-05-05 | 2010-11-11 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3346629A (en) | 1963-08-15 | 1967-10-10 | Monsanto Co | Process for preparing beta-ethylenically unsaturated organic sulfonates |
ZA672362B (ja) * | 1965-08-04 | |||
US3708437A (en) * | 1969-12-04 | 1973-01-02 | Chevron Res | 2-olefin sulfonate for liquid detergents |
US3860528A (en) | 1970-06-10 | 1975-01-14 | Ethyl Corp | Chemical composition containing mixed olefins |
JPS4978706A (ja) * | 1972-11-27 | 1974-07-30 | ||
JPS5556196A (en) * | 1978-10-20 | 1980-04-24 | Lion Fat Oil Co Ltd | Liquid detergent composition |
JPS5655498A (en) * | 1979-10-11 | 1981-05-16 | Lion Corp | Detergent composition |
US4507233A (en) * | 1981-04-22 | 1985-03-26 | Oriental Yeast Co., Ltd. | Colored molecular weight marker |
GB8817293D0 (en) * | 1988-07-20 | 1988-08-24 | Shell Int Research | Process for preparation of internal olefin sulphonates |
ZA986448B (en) | 1997-07-21 | 1999-01-21 | Procter & Gamble | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
JP2001072655A (ja) * | 1999-09-08 | 2001-03-21 | Lion Corp | インナーオレフィンスルホン酸とインナーオレフィンスルホネートの製造方法およびインナーオレフィンスルホン酸の製造装置 |
JP2001114749A (ja) * | 1999-10-14 | 2001-04-24 | Lion Corp | インナーオレフィンスルホネートの製造方法 |
JP2001247534A (ja) * | 1999-12-27 | 2001-09-11 | Lion Corp | インナーオレフィンスルホネートの製造方法 |
US8387953B2 (en) | 2009-05-05 | 2013-03-05 | Mojack Distributors, Llc | Apparatuses and methods for an improved vehicle jack having a screw jack assembly |
US8318143B2 (en) * | 2010-09-02 | 2012-11-27 | Kelly Van Gogh Hair Colour Cosmetics, Inc. | Compositions for treating keratin-containing fibers and maintaining dyed fiber color integrity |
JP6243673B2 (ja) | 2012-09-20 | 2017-12-06 | 花王株式会社 | 内部オレフィンスルホン酸塩組成物及びこれを含有する洗浄剤組成物 |
JP6300477B2 (ja) | 2012-09-20 | 2018-03-28 | 花王株式会社 | 皮膚又は毛髪用洗浄剤組成物 |
JP6235844B2 (ja) * | 2012-09-20 | 2017-11-22 | 花王株式会社 | 皮膚又は毛髪用洗浄剤組成物 |
JP6215629B2 (ja) | 2012-09-20 | 2017-10-18 | 花王株式会社 | 内部オレフィンスルホン酸塩組成物及びこれを含有する洗浄剤組成物 |
US20140080751A1 (en) | 2012-09-20 | 2014-03-20 | Kao Corporation | Internal olefinic sulfonate composition and cleansing composition containing the same |
US20140079660A1 (en) | 2012-09-20 | 2014-03-20 | Kao Corporation | Cleansing composition for skin or hair |
US20140080746A1 (en) | 2012-09-20 | 2014-03-20 | Kao Corporation | Cleansing composition for skin or hair |
JP6224390B2 (ja) | 2012-09-20 | 2017-11-01 | 花王株式会社 | 内部オレフィンスルホン酸塩組成物及びこれを含有する洗浄剤組成物 |
BR112015018423A2 (pt) * | 2013-02-13 | 2017-07-18 | Kao Corp | composição de olefina sulfonato interna |
-
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- 2014-01-31 WO PCT/JP2014/052258 patent/WO2014125940A1/ja active Application Filing
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- 2014-01-31 EP EP14752017.5A patent/EP2957625B1/en not_active Not-in-force
- 2014-01-31 US US14/766,059 patent/US9622952B2/en active Active
-
2017
- 2017-03-06 US US15/450,847 patent/US9877907B2/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58157758A (ja) * | 1982-03-15 | 1983-09-19 | Lion Corp | 高濃度オレフインスルホン酸塩溶液の製造法 |
JPH0257598B2 (ja) | 1982-08-10 | 1990-12-05 | Lion Corp | |
JPS59222466A (ja) * | 1983-05-31 | 1984-12-14 | Lion Corp | オレフインのスルホン化方法 |
JPS6032759A (ja) | 1983-07-29 | 1985-02-19 | Lion Corp | 内部オレフインスルホン酸塩の製造方法 |
JPS61134366A (ja) | 1984-12-06 | 1986-06-21 | Lion Corp | 界面活性剤中の油分分離方法 |
JP2625150B2 (ja) | 1988-04-21 | 1997-07-02 | ライオン株式会社 | インナーオレフィンスルホネートの製法 |
US5078916A (en) | 1989-01-03 | 1992-01-07 | Shell Oil Company | Detergent composition containing an internal olefin sulfonate component having an enhanced content of beta-hydroxy alkane sulfonate compounds |
JPH03126793A (ja) * | 1989-10-06 | 1991-05-29 | Unilever Nv | 洗剤組成物 |
JPH03126795A (ja) * | 1989-10-11 | 1991-05-29 | Lion Corp | 高濃度オレフィンスルホン酸塩水性スラリーの製造方法 |
JP2003081935A (ja) | 2001-09-10 | 2003-03-19 | Lion Corp | 内部オレフィンスルホン酸塩及びそれを含む洗浄剤組成物 |
WO2010129051A1 (en) | 2009-05-05 | 2010-11-11 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
Non-Patent Citations (2)
Title |
---|
J. AM. OIL CHEM. SOC., vol. 69, 1992, pages 39 |
TENSIDE SURF. DET., vol. 31, no. 5, 1994, pages 299 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014177620A (ja) * | 2013-02-13 | 2014-09-25 | Kao Corp | 内部オレフィンスルホン酸塩組成物 |
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BR112015018423A2 (pt) | 2017-07-18 |
US20170172881A1 (en) | 2017-06-22 |
EP2957625A4 (en) | 2016-07-20 |
US9877907B2 (en) | 2018-01-30 |
US9622952B2 (en) | 2017-04-18 |
CN104937088A (zh) | 2015-09-23 |
JP2014177620A (ja) | 2014-09-25 |
EP2957625A1 (en) | 2015-12-23 |
CN104937088B (zh) | 2018-07-03 |
US20150366775A1 (en) | 2015-12-24 |
EP2957625B1 (en) | 2018-07-18 |
JP6231393B2 (ja) | 2017-11-15 |
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