INTERNAL OLEFINE SULPHONATE COMPOSITION AND CLEANING COMPOSITION CONTAINING THE SAME

专利摘要:
abstract "internal olefin sulfonate composition and cleaning composition containing it" an internal olefin sulfonate composition is provided, which is capable of exerting satisfactory foaming capacity together with satisfactory foam volume, foaming speed , foam dissipation property, foam quality, foam durability in the presence of sebo and volume of foam in the presence of tallow in tallow and a cleaning composition containing it. the internal olefin sulfonate composition of the present invention comprises (a) an internal olefin sulfonate having 16 carbon atoms and (b) an internal olefin sulphonate having 18 carbon atoms, wherein a ratio of the content of mass (a / b) of component (a) to component (b) is 75/25 to 90/10 and where a mass ratio (hydroxy form / olefin form) to a content of a hydroxy form in the internal olefin sulfonate of component (a) and component (b) for an olefin form content in the internal olefin sulfonate of component (a) and component (b) is 75/25 to 100 / 0.
公开号:BR112015004920B1
申请号:R112015004920-6
申请日:2013-09-19
公开日:2020-03-03
发明作者:Yohei Yoshikawa；Yoshinori Mitsuda；Hiroshi Hori；Yoshifumi Nishimoto；Yasuhiro Doi
申请人:Kao Corporation；
IPC主号:

专利说明:

“INTERNAL OLEFINE SULPHONATE COMPOSITION AND CLEANING COMPOSITION CONTAINING THE SAME”
FIELD OF THE INVENTION [001] The present invention relates to an internal olefin sulfonate composition useful as a base for a cleaning agent and to a cleaning composition containing it.
BACKGROUND OF THE INVENTION [002] Anionic surfactants, particularly alkyl sulfates and polyoxyalkylene alkyl sulfates, are excellent in detergent and foaming power and thus are widely used as cleaning ingredients for domestic or industrial use. An olefin sulfonate, particularly an internal olefin sulfonate obtained with an internal olefin that has a double bond within an olefin chain, not at its end, as a raw material, has been reported as one of the anionic surfactants.
[003] Such internal olefin sulfonate is, in general, obtained by sulfonation of an internal olefin through reactions with a gas containing sulfur trioxide gas, followed by neutralization and then hydrolysis of the resulting sulfonic acid. Internal olefin sulfonate is known to have satisfactory or similar biodegradability, but is still insufficient in basic performance as cleaning agents, including foaming capacity and foam quality, compared to general-purpose surfactants, such as esters of alkyl polyoxyalkylene sulfuric acid. Thus, further improvement in such basic performance was desired. The more people have been concerned with water savings in recent years, the added value of the foam dissipation property, in addition to the satisfactory foaming capacity, foam quality, foaming speed and foam durability in the presence tallow was also required for use as active ingredients in detergents for
Petition 870160043543, of 8/15/2016, p. 11/67
2/56 laundry, dishwashing detergents, shampoos or similar.
[004] Patent Document 1 discloses a specific internal olefin sulfonic acid for the purposes of solubilization capacity, penetration capacity and interfacial tension reduction capacity. This discloses that when used as a shampoo, it satisfactorily frictionless foams and achieves an improved sensation.
[005] Patent Document 2 describes an internal olefin sulfonate specific for the purposes of improving detergent power, and discloses examples of application to shampoos and the like, and Patent Document 3 also describes an aqueous liquid cleaning agent containing a specific internal olefin sulfonate and having a low fog point.
CITATION LIST
PATENT DOCUMENT
Patent Document 1 - JP-A-2003-81935
Patent Document 2 - US Patent No. 5,078,916 Patent Document 3 - US Patent No. 3,708,437 SUMMARY OF THE INVENTION [006] The present invention provides an internal olefin sulfonate composition comprising (A) an internal olefin sulfonate tendo16 carbon atoms and (B) an internal olefin sulfonate having 18 carbon atoms, wherein a ratio of the mass content (A / B) of component (A) to component (B) is 75/25 to 90/10, and wherein a mass ratio (hydroxy form / olefin form) of a content of a hydroxide form in the internal olefin sulfonate of component (A) and component (B) to a content of an olefin form in the sulfonate of internal olefin of component (A) and component (B) is 75/25 to 100/0.
[007] Furthermore, the present invention provides a cleaning composition comprising the internal olefin sulfonate composition mentioned above
Petition 870160043543, of 8/15/2016, p. 12/67
3/56 of.
DETAILED DESCRIPTION OF THE INVENTION [008] However, further refinement is still required for any of the compositions described in the documents to exercise satisfactory foaming capacity together with satisfactory foam quality, foaming speed, foam dissipation property and foam durability in the presence of high-level model tallow.
[009] Therefore, the present invention provides an internal olefin sulfonate composition that can exercise satisfactory foaming capacity together with satisfactory foam quality, foaming speed, foam dissipation property and foam durability in the presence of high-level model tallow and provides a cleaning composition containing it.
[010] The present inventor studied an aliphatic chain length in an internal olefin sulfonate, a reason for it and several other conditions, and consequently found that an internal olefin sulfonate composition that satisfies the satisfactory foaming ability , together with satisfactory foam quality, foaming speed, foam durability in the presence of model tallow and foam dissipation property can be obtained by adjusting the ratio between an internal olefin sulfonate having 16 carbon atoms and a sulfonate of internal olefin having 18 carbon atoms in a predetermined range. On the basis of these findings, the present invention has been completed.
[011] According to the present invention, it can provide an internal olefin sulfonate composition which can exert satisfactory foaming capacity together with satisfactory foaming volume, foaming speed, foam dissipation property, quality of foam, durability
Petition 870160043543, of 8/15/2016, p. 13/67
4/56 foam in the presence of tallow and volume of foam in the presence of tallow in high levels and provide a cleaning composition.
[012] In this report below, the present invention will be described in detail.
INTERNAL OLEFINE SULPHONATE COMPOSITION [013] The internal olefin sulfonate composition of the present invention includes (A) an internal olefin sulfonate having 16 carbon atoms and (B) an internal olefin sulfonate having 18 carbon atoms, where a ratio of the mass content (A / B) of the component (A) to the component (B) is 75/25 to 90/10.
[014] In the present invention, an internal olefin sulfonate is a sulfonate obtained by sulfonating an internal olefin (an olefin having a double bond within the olefin chain) as the raw material, followed by neutralization and then hydrolysis, as described above. It should be noted that the internal olefin above can also have a broad meaning, including a trace amount of the so-called α-olefin, where a double bond is present at the C-1 position of the carbon chain. That is, sulfonation of an internal olefin produces quantitatively β-sultone, some of which are converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkane sulfonate and olefin sulfonate in the process of neutralization and hydrolysis (by example, J. Am. Oil Chem. Soc. 69, 39 (1992)). In this report, the hydroxyl group of the obtained hydroxyalkane sulfonate is present within the alkane chain and the double bond of the olefin sulfonate is present within the olefin chain. In addition, the product obtained is mainly a mixture of the substances mentioned above, some of which may include a trace amount of hydroxyalkane sulfonate having a hydroxyl group at the end of the carbon chain or olefin sulfonate having a double bond at the end of the carbon chain. In the present specification, each of these products and a mixture of them are collectively referred to as internal olefin sulfonate. Hydroxyalkane sulfonate is referred to as the form
Petition 870160043543, of 8/15/2016, p. 14/67
5/56 hydroxy an internal olefin sulfonate (in this report below, it can also be referred to as SAH) and olefin sulfonate is referred to as the olefin form of an internal olefin sulfonate (in this report below, it can also be referred to as IOS).
[015] The ratio of mass content (A / B) of component (A) to component (B) contained in the internal olefin sulfonate composition of the present invention is 75/25 to 90/10 from the point of in view of the foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and foam volume in the presence of tallow, it is preferably 77 / 23 to 90/10, more preferably from 77/23 to 85/15 from the point of view of foaming speed, foam dissipation property and foam durability in the presence of sebum during hair washing, as well as foam dissipation property, and foam dissipation property during hand washing. In addition, the mass content ratio (A / B) of component (A) and component (B) is more preferably 75/25 to 85/15 and, even more preferably, 75/25 to 77/23 from the point of view of foam quality and foam durability in the presence of tallow during hair washing, as well as foam quality, foam durability in the presence of tallow during hand washing. In addition, the ratio of mass content (A / B) of component (A) to component (B) is more preferably 80/20 to 90/10 and, even more preferably, 85/25 to 90/10 from the point of view of foaming capacity, foam volume and foam volume in the presence of sebum during hair washing, as well as foaming capacity during hand washing.
[016] The ratio of mass content (A / B) of component (A) to component (B) in the composition of internal olefin sulfonate is a numerical value measured by high performance liquid chromatography-mass spectrometry (in this report
Petition 870160043543, of 8/15/2016, p. 15/67
6/56 below, abbreviated as HPLC-MS). Specifically, an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms are separated by HPLC, each of which is then identified by analysis with MS. From their peak HPLC-MS area, the ratio of the mass content (A / B) of the component (A) to the component (B) in the internal olefin sulfonate is obtained.
[017] The total content of component (A) and component (B) in the internal olefin sulfonate composition of the present invention is preferably 50% by weight or greater, more preferably 70% by weight or greater, more preferably , 80% by weight or greater, more preferably, 90% by weight or greater, more preferably, 95% by weight or greater, more preferably, 96.5% by weight or greater, and even more preferably 97% by weight or greater from the point of view of foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and foam volume in the presence of tallow . The upper limit of the total content of component (A) and component (B) is preferably 100% by weight from the point of view of foam dissipation property, foam quality and foam durability in the presence of tallow during hair washing, as well as foam quality and foam durability in the presence of tallow during hand washing.
[018] As is evident from the aforementioned production method, the sulfonate group in the internal olefin sulfonate of the present invention is present within the olefin or alkane chain. In the present invention, from the point of view of the foaming capacity, it is preferable that the content of an internal olefin sulfonate, where the sulfonate group is present at the C-2 position of the olefin or alkane chain is low, although the content of an internal olefin sulfonate, in which the sulfonate group is still present inside, is high. IS
Petition 870160043543, of 8/15/2016, p. 16/67
7/56 more preferable that the content of an internal olefin sulfonate, where the sulfonate group is present at the C-2 position of the olefin chain or alkane chain, is low, with respect to the above internal olefin sulfonates having 16 atoms carbon and 18 carbon atoms.
[019] The content of the internal olefin sulfonate, where a sulfonate group is present at a C-2 position in the internal olefin sulfonate (component (A) and component (B)) having 16 and 18 carbon atoms is preferably , 28% by weight or less, more preferably, 24% by weight or less, more preferably, 23% by weight or less, more preferably, 22% by weight or less, more preferably, 20% by weight or less, more preferably less than 20% by weight, more preferably 15% by weight or less, and even more preferably 12% by weight or less, in the total content of component (A) and component (B), from from the point of view of the foaming capacity, foam volume, foaming speed and foam dissipation property during hair washing, as well as foaming capacity and foam dissipation property during hand washing. In addition, the content is preferably 5% by weight or greater, more preferably 6% by weight or greater, more preferably 7% by weight or greater, more preferably 10% by weight or greater, more preferably 12 % by weight or greater, more preferably, 15% by weight or greater, more preferably, 20% by weight or greater and, even more preferably, 22% by weight or greater in the total content of component (A) and component (B ), from the point of view of foam quality and foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, foam quality and volume of foam in the presence of tallow during hand washing , as well as cost and productivity.
[020] Next, the content of the internal olefin sulfonate, where a sulfonate group is present at a C-2 position in the internal olefin sulfonate (component
Petition 870160043543, of 8/15/2016, p. 17/67
8/56 (A) and component (B)) having 16 and 18 carbon atoms is, in the total content of component (A) and component (B), preferably 5% by weight or greater and, preferably, 28% by weight by weight or less, more preferably, 12% by weight or greater and 22% by weight or less, more preferably, 12% by weight or greater and 20% by weight or less, more preferably, 15% by weight or greater and 20% by mass or less and, even more preferably, 15% by mass or greater and less than 20% by mass, from the point of view of foaming capacity, foaming volume, foaming speed, property of foam dissipation, foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, foaming ability, foam dissipation property, foam quality and foam durability in the presence of tallow during hand washing, as well as cost and productivity. In addition, the content is preferably 5% by weight or greater and preferably 15% by weight or less, more preferably 6% by weight or greater and 15% by weight or less, more preferably 7% by weight or greater and 15% by weight or less and, even more preferably, 7% by weight or greater and 12% by weight or less, from the point of view of foaming capacity, foam volume, foaming speed foam and foam dissipation property during hair washing, as well as foaming capacity and foam dissipation property during hand washing. In addition, the content is preferably 20% by weight or greater and 28% by weight or less, more preferably 23% by weight or greater and 28% by weight or less, in the total content of component (A) and component (B), from the point of view of foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, foam quality, foam durability in the presence of tallow during hand washing, as well as cost and productivity.
Petition 870160043543, of 8/15/2016, p. 18/67
9/56 [021] In addition, the content of α-olefin sulfonate, where the sulfonate group is positioned at the C-1 position of an olefin chain or an alkane chain, is in the total content of component (A) and component (B), preferably less than 2.8% by weight, more preferably 0.01% by weight or greater and less than 2.8% by weight, more preferably 0.1% by weight or greater than and less than 2.8% by weight and, even more preferably, 0.3% by weight or greater and less than 2.8% by weight from the point of view of the foaming capacity and property of foam dissipation.
[022] It should be noted that the content of the internal olefin sulfonate, where the sulfonate group is present at the C-2 position in the internal olefin sulfonate having 16 and 18 carbon atoms, can be measured by a method, such as spectroscopy of nuclear magnetic resonance. More specifically, it is a numerical value measured by a method using gas chromatography described later in the Example.
[023] The ratio of the mass content (hydroxy form / olefin form) of the hydroxy form to the olefin form in the internal olefin sulfonate (component (A) and component (B)) having 16 and 18 carbon atoms is 75/25 to 100/0, preferably 75/25 to 95/5, more preferably, 80/20 to 95/5 from the point of view of foaming capacity, foam volume, forming speed foam, foam dissipation property, foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, as well as foaming capacity, foam dissipating property, quality of foam and foam durability in the presence of tallow during hand washing.
[024] The ratio of the mass content of the hydroxy form to the olefin form in the internal olefin sulfonate having 16 and 18 carbon atoms of the present invention can be measured by the method described later in the Examples.
Petition 870160043543, of 8/15/2016, p. 19/67
10/56 [025] As the internal olefin sulfonate composition of the present invention is obtained by sulfonating an internal olefin, followed by neutralization and hydrolysis, as described above, an internal olefin of unreacted raw material and inorganic compounds can remain in the composition. It is preferred that the contents of these components are much lower.
[026] The content of the internal olefin of raw material in the internal olefin sulfonate composition of the present invention is preferably less than 5.0% by weight, more preferably less than 3.0% by weight, more preferably less than 1.5% by weight, and even more preferably less than 1.0% by weight with respect to the amount of the internal olefin sulfonates from the point of view of the foaming capacity, volume foam, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, as well as foaming ability, property of foam dissipation, foam quality and foam durability in the presence of tallow during hand washing.
[027] The content of unreacted internal olefin can be measured by a method described later in the Examples.
[028] The content of inorganic compounds in the internal olefin sulfonate composition of the present invention is preferably less than 7.5% by weight, more preferably less than 5.0% by weight, more preferably less than than 3.0% by weight, more preferably less than 2.0% by weight and, even more preferably, less than 1.6% by weight with respect to the amount of the internal olefin sulfonates from the point of view foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and foam volume in the presence of tallow during hair washing,
Petition 870160043543, of 8/15/2016, p. 20/67
11/56 as well as foaming capacity, foam dissipation property, foam quality and foam durability in the presence of tallow during hand washing.
[029] In this context, inorganic compounds include sulfates and alkaline agents. The content of these inorganic compounds can be measured by potentiometric titration. Specifically, the content can be measured by a method described later in the Examples.
[030] The internal olefin sulfonate composition of the present invention can contain a hydroxy form and an olefin form having any number of carbon atoms that are different from that of component (A) and component (B). The numbers of carbon atoms in the form of hydroxy and in the form of olefin, except for component (A) and component (B), are preferably 8 to 15, 17 and 19 to 24, more preferably, 12, 14 and 20, more preferably, 12 and 14 and, even more preferably, 14 from the point of view of foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, as well as foaming capacity, foam dissipation property, foam quality and foam durability in the presence of tallow during the washing of the hair hand. These hydroxy forms and olefin forms having various numbers of carbon atoms are derived from the internal olefin used as a raw material.
[031] The internal olefin sulfonate composition of the present invention may contain other components, for example, water as a medium, a pH adjuster, a viscosity reducing agent, an organic solvent and polyhydric alcohols, in addition to the components described above.
METHOD FOR PRODUCING SULPHONATE COMPOSITION OF
Petition 870160043543, of 8/15/2016, p. 21/67
12/56
INTERNAL OLEFINE [032] The internal olefin sulfonate composition can be produced by sulfonating an internal olefin of raw material having 8 to 24 carbon atoms, followed by neutralization and hydrolysis. More specifically, for example, the composition can be produced according to the methods described in Patent Nos. 1633184 and 2625150, and Tenside Surf. Det. 31 (5) 299 (1994), and the like.
[033] As mentioned above, in the present invention, an internal raw material olefin refers to an olefin having substantially a double bond within the olefin chain. The content of α-olefin, where a double bond is present at a C-1 position in the internal raw material olefin is preferably less than 2.8% by weight, more preferably 0.01% by weight or greater and less than 2.8% by mass, more preferably 0.1% by mass or greater and less than 2.8% by mass, and even more preferably 0.3% by mass or greater and less than 2.8% by weight from the point of view of foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, as well as foaming capacity, foam dissipation property, foam quality and foam durability in the presence of tallow during hand washing. From the point of view of the foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of tallow and foam volume in the presence of tallow during hair washing, as well as foaming capacity, foam dissipation property, foam quality and foam durability in the presence of sebum during hand washing of the obtained internal olefin sulfonate composition, the number of carbon atoms in the internal olefin is preferably 8 to 24, more
Petition 870160043543, of 8/15/2016, p. 22/67
13/56 preferably from 12 to 20, more preferably from 12 to 18, more preferably from 14 to 18, and even more preferably from 16 to 18. An internal olefin that will be used as a raw material can be only used, or a combination of two or more may be used.
[034] When the internal olefin sulfonate composition is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal olefin, where the double bond is present at the C-2 position in the olefin internal raw material is preferably 48% by weight or less, more preferably 40% by weight or less, more preferably 35% by weight or less, more preferably 33% by weight or less, more preferably 30 % by mass or less, more preferably, 28% by mass or less, more preferably, 23% by mass or less, more preferably, 20% by mass or less, more preferably, less than 20% by mass and, even more preferably 18% by weight or less from the point of view of foaming capacity, foam volume, foaming speed and foam dissipation property during hair washing, as well as foaming capacity and property d and foam dissipation during hand washing. Furthermore, the content is preferably 5% by weight or greater, more preferably 7% by weight or greater, more preferably 10% by weight or greater, more preferably 15% by weight or greater, more preferably 20 % by weight or greater, more preferably, 23% by weight or greater, more preferably, 33% by weight or greater, and, even more preferably, 35% by weight or greater, from the point of view of foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, foam quality and volume of foam in the presence of tallow during hand washing, as well as cost and productivity.
[035] Then, when the internal olefin sulfonate composition is obtained
Petition 870160043543, of 8/15/2016, p. 23/67
14/56 by sulfonation of the internal olefin of the raw material, followed by neutralization and hydrolysis, the content of an internal olefin, in which the double bond is present at the C-2 position in the internal olefin of the raw material is preferably 5 % by weight or greater and 48% by weight or less, more preferably, 15% by weight or greater and 48% by weight or less, more preferably, 18% by weight or greater and 40% by weight or less, and further more preferably, 20% by weight or greater and 35% by weight or less, from the point of view of foaming capacity, foam volume, foaming speed, foam dissipation property, foam quality, volume of foam in the presence of tallow, and durability of foam in the presence of tallow during hair washing, foaming capacity, foam quality and volume of foam in the presence of tallow during hand washing, as well as cost and productivity . In addition, the content is preferably 5% by weight or greater and 23% by weight or less, more preferably 7% by weight or greater and 23% by weight or less, more preferably 10% by weight or greater and 20% by weight or less, more preferably, 10% by weight or greater and less than 20% by weight, and, even more preferably, 15% by weight or greater and 18% by weight or less from the point of view. foaming capacity, foam volume, foaming speed, foam dissipation property and foam durability in the presence of sebum during hair washing, as well as foaming capacity during hand washing. Furthermore, the content is preferably 33% by weight or greater and 48% by weight or less, more preferably 35% by weight or greater and 48% by weight or less, and even more preferably 40% by weight or greater and 48% by mass or less from the point of view of foam quality, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, quality of the foam, volume of foam in the presence of sebum during hand washing, as well
Petition 870160043543, of 8/15/2016, p. 24/67
15/56 as cost and productivity.
[036] In the synthesis of the internal olefin sulfonate composition, the content of the internal olefin of raw material, in which the double bond is present at position C-2 in the internal olefin of raw material, can be measured, for example, by gas chromatography-mass spectrometry (in this report below, abbreviated as GC-MS). Specifically, components having different carbon chain lengths and double bond positions are precisely separated by a gas chromatography analyzer (in this report below, abbreviated as GC), and each component is then analyzed by mass spectrometry (in this report below, abbreviated as MS) to identify the position of the double bond. From the numerical value resulting from the peak area of the GC, the fraction of each component is found.
[037] The raw material internal olefin may contain a paraffin component. The content of the paraffin component is preferably less than 5% by weight and, more preferably, less than 3% by weight from the point of view of foaming capacity, foam dissipating property, quality of foam, foam durability in the presence of tallow and volume of foam in the presence of tallow during hair washing, as well as foam dissipation property, foam quality and foam durability in the presence of tallow during hand washing.
[038] The content of the paraffin component can be measured, for example, by GCMS.
[039] The sulfonation reaction can be carried out by reacting a sulfur trioxide gas with an internal olefin in a ratio of 1 to 1.2 moles of sulfur trioxide per mol of the internal olefin of the raw material. The reactions can be carried out at a reaction temperature of 20 to 40 ° C.
[040] Neutralization is carried out by reacting 1 to 1.5 times the amount
Petition 870160043543, of 8/15/2016, p. 25/67
16/56 molar of an alkaline aqueous solution, such as sodium hydroxide, potassium hydroxide, ammonia or 2-aminoethanol with the theoretical value of the sulfonate group.
[041] The hydrolysis reaction can be carried out at 90 to 200 ° C for 30 minutes to three hours in the presence of water. These reactions can be carried out successively. In addition, after the completion of the reactions, the products can be purified by extraction, washing or the like.
[042] Furthermore, in the production of the internal olefin sulfonate composition, the internal olefin of raw material, in which the number of carbon atoms is distributed from 8 to 24, can be subjected to sulfonation, neutralization and hydrolysis or the internal olefin of raw material having a uniform number of carbon atoms can be subjected to sulfonation, neutralization and hydrolysis. In addition, a plurality of internal olefin sulfonates having different numbers of carbon atoms can be produced in advance and then mixed, as needed.
[043] The internal olefin sulfonate composition of the present invention exerts satisfactory foaming capacity together with satisfactory foaming volume, foaming speed, foam dissipation property, foam quality, foam durability in the presence of sebum and foam volume in the presence of high levels of sebum, and is thus useful as a cleaning ingredient. Specifically, the internal olefin sulfonate composition of the present invention can be used in household cleaning agents, such as hair shampoos, body cleaners, laundry detergents, and kitchen detergents, and is particularly useful as a base for shampoo. for hair.
CLEANING COMPOSITION [044] The cleaning composition of the present invention is not particularly limited, as long as the cleaning composition contains the sulfonate composition
Petition 870160043543, of 8/15/2016, p. 26/67
17/56 of internal olefin of the present invention. The cleaning composition of the present invention may contain other components depending on the intended purpose. Examples of the other components include another surfactant, a foaming agent and an auxiliary agent. The content of the internal olefin sulfonate composition in the cleaning composition is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, and even more preferably 2 to 30% by weight. mass, in terms of the amount of internal olefin sulfonates.
[045] The other surfactant is preferably, for example, alkyl sulfate and polyoxyalkylene alkyl sulfate. Examples of the auxiliary agent include, but are not particularly limited to, water, polymer, a solution in oil, silicone, a wetting agent, a viscosity regulator, a preservative, an anti-inflammatory agent, an antioxidant, an ultraviolet absorber, a sequestering agent , a pearly agent, a dye, a fragrance, an enzyme, a whitening agent, a whitening activator and pH adjuster.
[046] The cleaning composition of the present invention can be produced, for example, by mixing the internal olefin sulfonate composition and the components described above.
[047] In the following, the present invention and preferred embodiments of the present invention will be described.
- An internal olefin sulfonate composition comprising (A) an internal olefin sulfonate having 16 carbon atoms and (B) an internal olefin sulfonate having 18 carbon atoms, wherein a mass content ratio (A / B) from component (A) to component (B) is 75/25 to 90/10, and in which a mass ratio (hydroxy form / olefin form) to a content of a hydroxy form in the internal olefin sulfonate of component (A) and component (B) for an olefin form content in the internal olefin sulfonate of component (A) and component (B) is 75/25 to 100/0.
Petition 870160043543, of 8/15/2016, p. 27/67
18/56
- The internal olefin sulfonate composition according to 1, wherein the ratio of the mass content (A / B) of the component (A) to the component (B) in the internal olefin sulfonate composition is preferably 77/23 to 90/10, more preferably from 77/23 to 85/15, and preferably from 75/25 to 85/15, more preferably from 75/25 to 77/23, and preferably from 80/20 to 90/10, more preferably, 85/25 to 90/10.
- The internal olefin sulfonate composition, according to 1 or 2, in which a total content of component (A) and component (B) in the internal olefin sulfonate composition is preferably 50% by weight or greater, more preferably, 70% by weight or greater, more preferably, 80% by weight or greater, more preferably, 90% by weight or greater, more preferably, 95% by weight or greater, more preferably, 96.5% by weight or greater , and, even more preferably, 97% by mass or greater, with its upper limit being 100% by mass.
- The composition of internal olefin sulfonate, according to any one from 1 to 3, in which the content of the internal olefin sulfonate in which a sulfonate group is present at a C-2 position in the internal olefin sulfonate (component (A ) and component (B)) having 16 and 18 carbon atoms is preferably 28% by weight or less, more preferably 24% by weight or less, more preferably 23% by weight or less, more preferably 22% by mass or less, more preferably, 20% by mass or less, even more preferably, less than 20% by mass, and, preferably, 5% by mass or greater, more preferably, 6% by mass or greater, more preferably , 7% by weight or greater, more preferably, 10% by weight or greater, more preferably, 12% by weight or greater, more preferably, 15% by weight or greater, more preferably, 20% by weight or greater, and, even more preferably, 22% by mass or greater.
- The composition of internal olefin sulfonate, according to any one from 1 to 4, in which an internal olefin sulfonate content in which a group
Petition 870160043543, of 8/15/2016, p. 28/67
19/56 sulfonate is present at a C-2 position in the internal olefin sulfonate (component (A) and component (B)) having 16 and 18 carbon atoms is preferably 5% by weight or greater and preferably 28 % by weight or less, more preferably, 12% by weight or greater and 22% by weight or less, more preferably, 12% by weight or greater and 20% by weight or less, more preferably, 15% by weight or greater and 20% by mass or less, and even more preferably 15% by mass or greater and less than 20% by mass.
- The internal olefin sulfonate composition, according to any one between 1 and 5, in which an internal olefin sulfonate content in which a sulfonate group is present at a C-2 position in the internal olefin sulfonate (component (A ) and component (B)) having 16 and 18 carbon atoms is preferably 5% by weight or greater and preferably 15% by weight or less, more preferably 6% by weight or greater and 15% by weight or less, more preferably, 7% by weight or greater and 15% by weight or less, and even more preferably, 7% by weight or greater and 12% by weight or less.
- The composition of internal olefin sulfonate, according to any one from 1 to 6, in which an internal olefin sulfonate content in which a sulfonate group is present at a C-2 position in the internal olefin sulfonate (component (A ) and component (B)) having 16 and 18 carbon atoms is preferably 20% by weight or greater and 28% by weight or less, more preferably 23% by weight or greater and 28 by weight or less.
- The internal olefin sulfonate composition, according to any one from 1 to 7, wherein a ratio of the mass content of a hydroxy form to an olefin form (hydroxy form / olefin form) in the olefin sulfonate internal having 16 and 18 carbon atoms is preferably 75/25 to 95/5, more preferably 80/20 to 95/5.
- The composition of internal olefin sulfonate, according to any
Petition 870160043543, of 8/15/2016, p. 29/67
20/56 one between 1 to 8, wherein an internal olefin content of raw material in the internal olefin sulfonate composition is preferably less than 5.0% by weight, more preferably less than 3, 0 wt%, more preferably less than 1.5 wt%, and even more preferably less than 1.0 wt% with respect to the amount of the internal olefin sulfonates.
- The internal olefin sulfonate composition, according to any one from 1 to 9, wherein a content of inorganic compounds in the internal olefin sulfonate composition is preferably less than 7.5% by mass, more preferably, less than 5.0% by mass, more preferably less than 3.0% by mass, more preferably less than 2.0% by mass, even more preferably less than 1.6% by mass with respect the amount of the internal olefin sulfonates.
- The composition of internal olefin sulfonate, according to any one between 1 and 10, in which the numbers of carbon atoms in a hydroxy form and an olefin form having carbon atoms, except component (A) and component ( B) in the internal olefin sulfonate composition is preferably 8 to 15, 17 and 19 to 24, more preferably 12, 14 and 20, more preferably 12 and 14, and even more preferably 14 .
- The internal olefin sulfonate composition, according to any one from 1 to 11, preferably obtained by sulphonating an internal raw material olefin composition containing an internal raw material olefin, followed by neutralization and then hydrolysis, wherein an internal olefin content of raw material in which a double bond is present at a C-2 position is 48% by weight or less.
- The internal olefin sulfonate composition, according to any one from 1 to 12, obtained by sulfonation of an internal raw material olefin composition containing an internal raw material olefin, followed by neutralization
Petition 870160043543, of 8/15/2016, p. 30/67
21/56 and then hydrolysis, where an internal olefin content of raw material in which a double bond is present at a C-2 position is less than 20% by weight.
- The composition of internal olefin sulfonate, according to any one from 1 to 13, in which when the composition of internal olefin sulfonate is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal raw material olefin in which the double bond is present at the C-2 position in the internal raw material olefin is preferably 40% by weight or less, more preferably 35% by weight or less, more preferably, 33% by mass or less, more preferably, 30% by mass or less, more preferably, 28% by mass or less, more preferably, 23% by mass or less, more preferably, 20% by mass or less, more preferably, less than 20% by weight and, even more preferably, 18% by weight or less.
- The composition of internal olefin sulfonate, according to any one from 1 to 14, in which when the composition of internal olefin sulfonate is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal raw material olefin in which the double bond is present at the C-2 position in the internal raw material olefin is preferably 5% by weight or greater, more preferably 7% by weight or greater, more preferably, 10% by weight or greater, more preferably, 15% by weight or greater, more preferably, 20% by weight or greater, more preferably, 23% by weight or greater, more preferably, 33% by weight or greater, and yet more preferably, 35% by weight or greater.
- The composition of internal olefin sulfonate, according to any one from 1 to 15, in which when the composition of internal olefin sulfonate is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal raw material olefin where the double bond is
Petition 870160043543, of 8/15/2016, p. 31/67
22/56 present at position C-2 in the internal olefin of raw material is preferably 5% by weight or greater and 48% by weight or less, more preferably, 15% by weight or greater and 48% by weight or less more preferably 18% by weight or greater and 40% by weight or less, and even more preferably 20% by weight or greater and 35% by weight or less.
- The composition of internal olefin sulfonate, according to any one from 1 to 16, in which when the composition of internal olefin sulfonate is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal raw material olefin in which the double bond is present at the C-2 position in the internal raw material olefin is preferably 5% by weight or greater and 23% by weight or less, more preferably 7% by weight. mass or greater and 23% by mass or less, more preferably, 10% by mass or greater and 20% by mass or less, more preferably, 10% by mass or greater and less than 20% by mass, and even more preferably 15% by weight or greater and 18% by weight or less.
- The composition of internal olefin sulfonate, according to any one from 1 to 17, in which when the composition of internal olefin sulfonate is obtained by sulfonation of the internal olefin of raw material, followed by neutralization and hydrolysis, the content of an internal raw material olefin in which the double bond is present at the C-2 position in the internal raw material olefin is preferably 33% by weight or greater and 48% by weight or less, more preferably 35% by weight. mass or greater and 48% by mass or less, and even more preferably 40% by mass or greater and 48% by mass or less.
- A cleaning composition comprising the composition of internal olefin sulfonate, according to any one from 1 to 18.
The cleaning composition according to 19, in which the content of the internal olefin sulfonate composition is preferably 0.1 to 80% by weight.
Petition 870160043543, of 8/15/2016, p. 32/67
23/56
The cleaning composition according to 19 or 20, further comprising one or more preferably selected from an alkyl sulfate and a polyoxyalkylene alkyl sulfate.
- A method for washing the hair, comprising applying the cleaning composition of anyone between 19 to 21 above on the hair, followed by washing and then rinsing.
- A method for washing the skin, comprising applying the cleaning composition of anyone between 19 to 21 above on the skin, followed by washing and then rinsing.
- A method to improve the durability of the foam in the presence of model tallow, comprising applying the cleaning composition of anyone between 19 to 21 above on hair or skin.
- A method for improving the foam dissipation property and foam quality, comprising applying the cleaning composition of anyone between 19 to 21 above on the hair or skin.
- A method for improving the volume of foam, comprising applying the cleaning composition of anyone between 19 to 21 above on the hair.
- The cleaning composition of anyone between 19 to 21 above to wash your hair.
- The cleaning composition of anyone between 19 to 21 above to wash the skin.
- Use of the cleaning composition of anyone between 19 to 21 above to wash the hair.
- Use of the cleaning composition of anyone between 19 to 21 above to wash the skin.
- The cleaning composition of anyone between 19 to 21 above to improve the durability of the foam in the presence of model sebum in the hair or skin.
Petition 870160043543, of 8/15/2016, p. 33/67
24/56
- Use of the cleaning composition of anyone between 19 to 21 above to improve the durability of the foam in the presence of model sebum in hair or skin.
- Use of the cleaning composition of anyone between 19 to 21 above to improve the foam dissipation property and foam quality when applied to hair or skin.
- Use of the cleaning composition of anyone between 19 to 21 above to improve the volume of foam when applied to hair or skin.
EXAMPLES [048] In this report below, the present invention will be specifically described with reference to the Examples. It should be noted that, unless otherwise specifically noted, the content of each of the components is expressed by mass% in the following Tables. In addition, the methods for measuring various physical properties are as follows.
(1) Measurement conditions (i) Method for measuring the position of a double bond in the internal olefin [049] The position of a double bond in an internal olefin was measured by gas chromatography (in this report below, abbreviated as GC). Specifically, an internal olefin was converted to a derivative dictated by reaction with dimethyl disulfide and then each component was separated by GC. The position of a double bond in an internal olefin was discovered based on the peak area of each component.
[050] The apparatus and analytical conditions used for the measurement are as follows: GC apparatus (trade name: HP6890, the product of the Hewlett-Packard Company); Column (trade name: Ultra-Liga-1 HT capillary column, 30 m x 250 pm x 0.15 pm, the product of Frontier Laboratories Ltd.); Detector (hydrogen flame ionization detector (FID)); Injection temperature of 300 ° C; Temperature of
Petition 870160043543, of 8/15/2016, p. 34/67
25/56 350 ° C tector; and He flow rate of 4.6 mL / min.
(ii) Method to measure the content of internal olefin sulfonate, where a sulfonate group is present at a C-2 position [051] The binding position of the sulfonate group was measured by GC. Specifically, the internal olefin sulfonate was reacted with trimethylsilyldiazomethane to form a methyl esterified derivative. Then, each component was separated by GC. Each peak area was considered as a mass ratio, and the internal olefin sulfonate content, in which a sulfonate group is present at a C-2 position, was quantified.
[052] The apparatus and analytical conditions used for the measurement are as follows: GC apparatus (trade name: Agilent 6850 technology, the product of Agilent Technologies, Inc.); Column (trade name: HP-1 capillary column, 30 m x 320 pm x 0.25 pm, the product of Agilent Technologies, Inc.); Detector (hydrogen flame ionization detector (FID)); Injection temperature of 300 ° C; Detector temperature of 300 ° C; He flow rate of 1.0 mL / min .; oven (60 ° C (0 min.) 10 ° C / min. 300 ° C (10 min.)).
(iii) Method to measure the mass ratio of the hydroxy form / olefin form [053] The mass ratio of the hydroxy form / olefin form was measured by HPLC-MS. Specifically, the hydroxy form and the olefin form were separated by HPLC and each form was identified by separate analysis with MS. From the resulting HPLC-MS peak area, the fraction of each form was obtained.
[054] The apparatus and analytical conditions used for the measurement are as follows: HPLC apparatus (trade name: Agilent 1100 technology, the product of Agilent Technologies, Inc.); Column (trade name: L-column ODS 4.6 x 150 mm, the product of the Chemical Evaluation and Research Institute, Japan); Sample preparation (diluted 1000 times with methanol); Eluent A (10 mM ammonium acetate in water);
Petition 870160043543, of 8/15/2016, p. 35/67
26/56
Eluent B (10 mM ammonium acetate in methanol), Gradient (0 min (A / B = 30/70%) min (30/70%) 55 min (0/100%) 65 min (0/100%) 66 min (30/70%) min (30/70%)); MS device (trade name: Agilent 1100 MS SL technology (G1946D)); and MS detection (anion detection m / z 60 to 1600, UV 240 nm).
(iv) Method to measure the content of the internal olefin of raw material [055] The content of the internal olefin of raw material was measured by GC. Specifically, ethanol and petroleum ether were added to an aqueous solution of internal olefin sulfonate, followed by extraction to provide olefin in the petroleum ether phase. From the peak area of the olefin GC, the amount of it was quantified.
[056] The apparatus and analytical conditions used for the measurement are as follows: GC apparatus (trade name: Agilent 6850 technology, the product of Agilent Technologies, Inc.); Column (trade name: Ultra-Alloy-1HT capillary column, 15 m x 250 pm x 0.15 pm, the product of Frontier Laboratories, Ltd.); Detector (hydrogen flame ionization detector (FID)); Injection temperature of 300 ° C; Detector temperature of 350 ° C; and He flow rate of 3.8 mL / min.
(v) Method for measuring the content of inorganic compounds [057] The content of inorganic compounds was measured by potentiometric titration and neutralization titration. Specifically, the Na2SO4 content was quantified by measuring sulfate ion (SO4 ^2- ) through potentiometric titration. In addition, the NaOH content was quantified by neutralization titration with dilute hydrochloric acid.
(vi) Method for measuring the content of the paraffin component [058] The content of the paraffin component was measured by GC. Specifically, ethanol and petroleum ether were added to an aqueous solution of internal olefin sulfonate, followed by extraction to provide paraffin in the petroleum ether phase. From the peak area of the paraffin GC, the amount of this was quantified.
Petition 870160043543, of 8/15/2016, p. 36/67
27/56 [059] It should be noted that the apparatus and analytical conditions used are the same as those used to measure the content of the internal raw material olefin.
(2) Production of an internal olefin [060] Production example A - Synthesis of internal olefins C16, in which 16.5% by mass of the double bonds were presented in position C-2 [061] In a flask with a stirrer, 7000 g (28.9 moles) of 1-hexadecanol (trade name: KALCOL 6098, the product of Kao Corporation), and as a solid acid catalyst, 700 g (10% by weight based on the raw material alcohol) of γ-alumina (STREM Chemicals, Inc.) was placed and the reactions were allowed to proceed for five hours at 280 ° C, while stirring and passing nitrogen (7000 mL / minute) through the system. The alcohol conversion ratio was 100% and the purity of the internal C16 olefin was 99.7% after completion of the reaction. The resulting crude internal olefin was transferred to a distillation flask and distilled at 136 to 160 ° C / 4.0 mmHg, whereby 100% pure internal olefin having 16 carbon atoms was obtained. The double bond distribution in the resulting internal olefin was 0.5% by mass in position C-1, 16.5% by mass in position C-2, 15.4% by mass in position C-3, 16.4% by mass in position C-4, 17.2% by mass in position C-5, 14.2% by mass in position C-6 and 19.8% by weight in total in positions C-7 and 8.
[062] Production Example B - Synthesis of C1 internal olefins, in which 16.9% by mass of double bonds were presented in position C-2 [063] In a flask with a stirrer, 7000 g (25.9 moles) 1-octadecanol (trade name: KALCOL 8098, the product of Kao Corporation), and as a solid acid catalyst, 1050 g (15% by weight based on the raw material alcohol) of γalumina (STREM Chemicals, Inc.) were placed and the reactions were allowed to proceed for 13 hours at 285 ° C, while stirring and passing nitrogen (7000
Petition 870160043543, of 8/15/2016, p. 37/67
28/56 mL / minute) through the system. The alcohol conversion rate was 100% and the purity of the internal C18 olefin was 98.5% after the completion of the reaction. The resulting crude internal olefin was transferred to a distillation flask and distilled at 148 to 158 ° C / 0.5 mmHg, whereby 100% pure internal olefin having 18 carbon atoms was obtained. The double bond distribution in the resulting internal olefin was 0.7% by mass in position C-1, 16.9% by mass in position C-2, 15.9% by mass in position C-3, 16.0% by mass in position C-4, 14.7% by mass in position C-5, 11.2% by mass in position C-6, 10.2% by mass in position C-7 and 14.6% by mass in total at positions C-8 and 9.
[064] Production Example C - Synthesis of C16 internal olefins, in which 30.4% by mass of the double bonds were presented in position C-2 [065] In a bottle with a stirrer, 7000 g (28.9 moles) of 1-hexadecanol (trade name: KALCOL 6098, the product of Kao Corporation) and as a solid acid catalyst, 700 g (10% by weight based on the raw material alcohol) of γ-alumina (STREM Chemicals, Inc. ) were placed and the reactions were allowed to proceed for three hours at 280 ° C, while stirring and passing nitrogen (7000 mL / minute) through the system. The alcohol conversion ratio was 100% and the purity of the internal C16 olefin was 99.6% after the completion of the reaction. The resulting crude internal olefin was transferred to a distillation flask and distilled at 136 to 160 ° C / 4.0 mmHg, whereby 100% pure internal olefin having 16 carbon atoms was obtained. The double bond distribution in the resulting internal olefin was 1.8% by mass in position C-1, 30.4% by mass in position C-2, 23.9% by mass in position C-3, 16.8% by mass in position C-4, 12.0% by mass in position C-5, 7.4% by mass in position C-6 and 7.8% by mass in total in positions C7 and 8.
[066] Production Example D - Synthesis of C18 internal olefins in which 31.3% by mass of the double bonds were presented in position C-2
Petition 870160043543, of 8/15/2016, p. 38/67
29/56 [067] In a bottle with a shaker, 7000 g (25.9 moles) of 1-octadecanol (trade name: KALCOL 8098, the product of Kao Corporation) and as a solid acid catalyst, 700 g (10 % by mass relative to the raw material alcohol) of γ-alumina (STREM Chemicals, Inc.) were placed and the reactions were allowed to proceed for 10 hours at 280 ° C, while stirring and passing nitrogen (7000 mL / minute) through the system. The alcohol conversion ratio was 100% and the purity of the internal C18 olefin was 98.2% after the completion of the reaction. The resulting crude internal olefin was transferred to a distillation flask and distilled at 148 to 158 ° C / 0.5 mmHg, whereby 100% pure internal olefin was obtained. The double bond distribution in the resulting internal olefin was 0.8% by mass in position C-1, 31.3% by mass in position C-2, 22.9% by mass in position C-3, 15.5% by mass in position C-4, 10.8% by mass in position C-5, 7.2% by mass in position C-6, 5.3% by mass in position C-7 and 6.2% by mass in total at positions C-8 and 9.
[068] Production Example E - Synthesis of C14 internal olefins, in which 31.8% by mass of double bonds were presented in position C-2 [069] A flask with an agitator was loaded with 6000 g (26.7 moles ) of 1tetradecene (product name: LINEALENE 14, the product of Idemitsu Kosan Co., Ltd.) and 180 g (3% by weight in relation to the amount of the raw material α-olefin) of the protonic β-zeolite (CP- 814E, Zeolyst Int.) As a solid acid catalyst, followed by reaction at 120 ° C for 20 hours with stirring. Subsequently, the crude internal olefins were transferred to a flask for distillation and distilled at 124 to 136 ° C / 7.5 mmHg, to obtain C14 internal olefins having 100% olefin purity. The double bond distribution of the resulting internal olefins was 1.3% by mass in a C-1 position, 31.8% by mass in a C-2 position, 23.8% by mass in a C-3 position, 21 , 0% by mass in a C-4 position, 8.6% by mass in a C-5 position, and 13.6% by weight in total in the C-6 and C-7 positions.
Petition 870160043543, of 8/15/2016, p. 39/67
30/56 [070] Production Example F - Synthesis of internal olefins C16 / 18 (mass ratio 79.4 / 20.6), in which 27.8% by mass of double bonds were presented in position C-2 [ 071] A reaction time was adjusted in the same way for Production Example C, to produce C16 internal olefin (the double bond distribution was 0.5% by mass in a C-1 position, 30.1% by mass in a C-2 position, 25.5% by mass in a C-3 position, 18.9% by mass in a C-4 position, 11.1% by mass in a C-5 position, 7, 0 mass% in a C-6 position and 7.0 mass% in total in the C-7 and C-8 positions). In addition, a reaction time was adjusted in the same way for Production Example D, so as to produce C18 internal olefin (the double bond distribution was 0.3% by mass in a C-1 position, 19.0 % by mass in a C-2 position, 17.6% by mass in a C-3 position, 17.4% by mass in a C-4 position, 14.9% by mass in a C-5 position, 12 , 3% by mass in a C-6 position, 8.8% by mass in a C-7 position and 9.8% by weight in total in positions C-8 and C-9). 11.9 kg of the resulting C16 internal olefin and 3.1 kg of the resulting C18 internal olefin were mixed to produce 15.0 kg of C16 / C18 internal olefin (mass ratio 79.4 / 20.6). The double bond distribution of the resulting internal olefin was 0.4% by mass in a C-position, 27.8% by mass in a C-2 position, 23.9% by mass in a C-3 position, 18.6 % by mass in a C-4 position, 11.9% by mass in a C-5 position, 8.1% by mass in a C-6 position, 4.6% by mass in a C-7 position, 3 , 8% by mass in a C-8 position and 1.0% by mass in a C-9 position.
[072] Production Example G - Synthesis of C16 / 18 internal olefins (mass ratio 79.4 / 20.6), in which 45.3% by mass of double bonds were presented in position C-2 [073] One reaction time was adjusted in the same way for Production Example C, so as to produce internal olefin C16 (the bond distribution
Petition 870160043543, of 8/15/2016, p. 40/67
31/56 double was 2.0% by mass in a C-1 position, 45.9% by mass in a C-2 position, 28.2% by mass in a C-3 position, 13.9% by mass in a C-4 position, 5.5% by weight in a C-5 position, 2.5% by weight in a C-6 position and 2.2% by weight in total in positions C-7 and C-8 ). In addition, a reaction time was adjusted in the same way for Production Example D, in order to produce C18 internal olefin (the double bond distribution was 2.1% by mass in a C-1 position, 43.2 % by mass in a C-2 position, 29.7% by mass in a C-3 position, 14.9% by mass in a C-4 position, 5.6% by mass in a C-5 position, 3 , 4 mass% in a C-6 position, 0.9 mass% in a C-7 position and 0.2 mass% in total in the C-8 and C-9 positions). 11.9 kg of the resulting internal olefin C16 and 3.1 kg of the resulting internal olefin C18 were mixed to produce 15.0 kg of internal olefin C16 / C18 (mass ratio 79.4 / 20.6). The double bond distribution of the resulting internal olefin was 2.1% by weight in a C-1 position, 45.3% by weight in a C-2 position, 28.5% by weight in a C-3 position, 14 , 1% by mass in a C-4 position, 5.5% by mass in a C-5 position, 2.6% by mass in a C-6 position, 1.0% by mass in a C-7 position , 0.9% by mass in a C-8 position and 0.02% by mass in a C-9 position.
[074] Production Example H - Synthesis of C16 / 18 internal olefins (mass ratio 79.4 / 20.6), in which 34.8% by mass of double bonds were presented in position C-2 [075] One reaction time was adjusted in the same way for Production Example A, so as to produce internal olefin C16 (a) (the double bond distribution was 0.4% by mass in a C-1 position, 15.3% by mass in a C-2 position, 13.7% by mass in a C-3 position, 15.2% by mass in a C-4 position, 18.4% by mass in a C-5 position, 15, 1% by mass in a C-6 position and 21.8% by weight in total in the C-7 and C-8 positions). In addition, a reaction time was adjusted in the same way for Production Example C, in order to
Petition 870160043543, of 8/15/2016, p. 41/67
32/56 produce C16 (b) internal olefin (double bond distribution was 2.0% by mass in a C-1 position, 45.9% by mass in a C-2 position, 28.2% by mass in a C-3 position, 13.9% by mass in a C-4 position, 5.5% by mass in a C-5 position, 2.5% by mass in a C-6 position and 2.2% in total mass in positions C-7 and C-8).
[076] Meanwhile, a reaction time was adjusted in the same way for Production Example B, so as to produce internal olefin C18 (a) (the double bond distribution was 0.3 mass% in a C position -1, 13.3% by mass in a C-2 position, 12.6% by mass in a C-3 position, 13.9% by mass in a C-4 position, 14.8% by mass in a position C-5, 13.7% by weight in a position C-6, 12.6% by weight in a position C-7 and 18.8% by weight in total in positions C-8 and C-9). In addition, a reaction time was adjusted in the same way for Production Example D, so as to produce C18 (b) internal olefin (the double bond distribution was 2.1 mass% at a C-1 position, 43.2% by mass in a C-2 position, 29.7% by mass in a C-3 position, 14.9% by mass in a C-4 position, 5.6% by mass in a C- position 5, 3.4 mass% in a C-6 position, 0.9 mass% in a C-7 position and 0.2 mass% in total in the C-8 and C-9 positions). 4.6 kg of the resulting internal olefin C16 (a) and 7.3 kg of the resulting internal olefin C16 (b) and 1.0 kg of the resulting internal olefin C18 (a) and 2.1 kg of the resulting internal olefin C18 (b) ) were mixed to produce 15.0 kg of internal C16 / C18 olefin (mass ratio 79.4 / 20.6). The double bond distribution of the resulting internal olefin was 1.9% by mass in a C-1 position, 34.8% by mass in a C-2 position, 23.1% by mass in a C-3 position, 14 , 4% by mass in a C-4 position, 9.8% by mass in a C-5 position, 7.0% by mass in a C-6 position, 4.4% by mass in a C-7 position , 4.0 mass% in a C-8 position and 0.6 mass% in a C-9 position.
[077] Production Example I - Synthesis of C16 / 18 internal olefins (ratio in
Petition 870160043543, of 8/15/2016, p. 42/67
33/56 mass 79.4 / 20.6), in which 30.1% by mass of the double bonds were presented in position C-2 [078] A reaction time was adjusted in the same way for Production Example A , in order to produce C16 (c) internal olefin (the double bond distribution was 0.4% by mass in a C-1 position, 15.3% by mass in a C-2 position, 13.7% by mass in a C-3 position, 15.2% by weight in a C-4 position, 18.4% by weight in a C-5 position, 15.1% by weight in a C-6 position and 21.8% in total in positions C-7 and C-8). In addition, a reaction time was adjusted in the same way for Production Example C, so as to produce internal olefin C16 (d) (the double bond distribution was 0.5% by mass in a C-1 position, 30.1% by mass in a C-2 position, 25.5% by mass in a C-3 position, 18.9% by mass in a C-4 position, 11.1% by mass in a C- position 5, 7.0 mass% in a C-6 position and 7.0 mass% in total in the C-7 and C-8 positions).
[079] Meanwhile, a reaction time was adjusted in the same way for Production Example B, so as to produce internal olefin C18 (c) (the double bond distribution was 0.3 mass% in a C position -1, 13.3% by mass in a C-2 position, 12.6% by mass in a C-3 position, 13.9% by mass in a C-4 position, 14.8% by mass in a position C-5, 13.7% by weight in a position C-6, 12.6% by weight in a position C-7 and 18.8% by weight in total in positions C-8 and C-9). In addition, a reaction time was adjusted in the same way for Production Example D, so as to produce C18 (d) internal olefin (the double bond distribution was 0.5% by mass in a C-1 position, 25.0% by weight in a C-2 position, 22.8% by weight in a C-3 position, 19.1% by weight in a C-4 position, 14.0% by weight in a C- position 5. 7.4% by mass in a C-6 position, 5.4% by mass in a C-7 position and 5.8% by weight in total in positions C-8 and C-9). 0.9 kg of the resulting internal olefin C16 (c) and 11.0 kg
Petition 870160043543, of 8/15/2016, p. 43/67
34/56 of the resulting internal olefin C16 (d) and 0.8 kg of the resulting internal olefin C18 (c) and
2.3 kg of the resulting C18 internal olefin (d) were mixed to produce 15.0 kg of C16 / C18 internal olefin (mass ratio 79.4 / 20.6). The resulting double bond distribution of the resulting internal olefin was 0.9% by weight in a C-1 position, 30.1% by weight in a C-2 position, 24.5% by weight in a C-3 position, 17 , 3% by mass in a C-4 position, 13.9% by mass in a C-5 position, 6.8% by mass in a C-6 position, 3.2% by mass in a C-7 position , 2.8% by weight in a C-8 position and 0.4% by weight in a C-9 position.
[080] Production Example J - Synthesis of C16 / 18 internal olefins (mass ratio 79.4 / 20.6), in which 25.8% by mass of double bonds were presented in position C-2 [081] One reaction time was adjusted in the same way as Production Example A, so as to produce internal olefin C16 (e) (the double bond distribution was 0.4% by mass in a C-1 position, 15.3% in mass in a C-2 position, 13.7% by mass in a C-3 position, 15.2% by mass in a C-4 position, 18.4% by mass in a C-5 position, 15.1 % by mass in a C-6 position and 21.8% by weight in total in positions C-7 and C-8). In addition, a reaction time was adjusted in the same manner as Production Example C, so as to produce internal olefin C16 (f) (the double bond distribution was 0.5% by mass in a C-1 position, 30 , 1% by mass in a C-2 position, 25.5% by mass in a C-3 position, 18.9% by mass in a C-4 position, 11.1% by mass in a C-5 position , 7.0% by mass in a C-6 position and 7.0% by weight in total in the C-7 and C-8 positions).
[082] Meanwhile, a reaction time was adjusted in the same manner as Production Example D, to produce internal olefin C18 (e) (the double bond distribution was 0.5% by mass in a C- position 1, 25.0% by weight in a C-2 position, 22.8% by weight in a C-3 position, 19.1% by weight in a powder
Petition 870160043543, of 8/15/2016, p. 44/67
35/56 position C-4, 14.0% by mass in a C-5 position, 7.4% by mass in a C-6 position, 5.4% by mass in a C-7 position and 5.8 % by mass in total at positions C-8 and C-9). 3.9 kg of the resulting C16 internal olefin (e) and 8.0 kg of the resulting C16 internal olefin (f) and 3.1 kg of the resulting C18 internal olefin (e) were mixed to produce 15.0 kg of C16 internal olefin (e) / C18 (mass ratio 79.4 / 20.6). The double bond distribution of the resulting internal olefin was 0.7% by mass in a C-1 position, 25.8% by mass in a C-2 position, 21.6% by mass in a C-3 position, 17 , 0% by mass in a C-4 position, 15.9% by mass in a C-5 position, 8.5% by mass in a C-6 position, 5.3% by mass in a C7 position, 4 , 7% by mass in a C-8 position and 0.5% by mass in a C-9 position.
[083] Production Example K - Synthesis of internal olefins C16 / 18 (mass ratio 79.4 / 20.6), in which 22.0% by mass of double bonds were presented in position C-2 [084] One reaction time was adjusted in the same way as Production Example A, so as to produce internal olefin C16 (g) (the double bond distribution was 0.4% by mass in a C-1 position, 15.3% in mass in a C-2 position, 13.7% by mass in a C-3 position, 15.2% by mass in a C-4 position, 18.4% by mass in a C-5 position, 15.1 % by mass in a C-6 position and 21.8% by weight in total in positions C-7 and C-8). In addition, a reaction time was adjusted in the same manner as Production Example C, to produce C16 (h) internal olefin (the double bond distribution was 0.5% by mass at a C-1.30 position , 1% by mass in a C-2 position, 25.5% by mass in a C-3 position, 18.9% by mass in a C-4 position, 11.1% by mass in a C-5 position , 7.0 mass% in a C-6 position, and 7.0 mass% in total in the C-7 and C-8 positions) and C16 (i) internal olefin (the double bond distribution was 0.6 % by mass in a C-1 position, 30.6% by mass in a C-2 position, 26.1% by mass in a C-3 position, 18.8% by mass in a C-4 position, 10 , 5% in
Petition 870160043543, of 8/15/2016, p. 45/67
36/56 mass in a C-5 position, 6.7% in mass in a C-6 position and 6.6% in total in positions C-7 and C-8).
[085] Meanwhile, a reaction time was adjusted in the same manner as Production Example B, to produce internal olefin C18 (f) (the double bond distribution was 0.3 mass% at a C- position) 1, 13.3% by mass in a C-2 position, 12.6% by mass in a C-3 position, 13.9% by mass in a C-4 position, 14.8% by mass in a position C-5, 13.7% by weight in a C-6 position, 12.6% by weight in a C-7 position and 18.8% by weight in total in positions C-8 and C-9). In addition, a reaction time was adjusted in the same manner as Production Example D, to produce C18 (g) internal olefin (the double bond distribution was 0.5% by mass at a C-1 position, 25 , 0% by mass in a C-2 position, 22,8% by mass in a C-3 position, 19,1% by mass in a C-4 position, 14,0% by mass in a C-5 position , 7,4% by mass in a C-6 position, 5,4% by mass in a C-7 position and 5,8% by weight in total in the C-8 and C-9 positions). 6.9 kg of the resulting C16 internal olefin (g), 1.2 kg of the resulting C16 internal olefin (h) and 3.8 kg of the resulting C16 internal olefin (i) and 0.8 kg of the resulting C18 internal olefin (f) ) and 2.3 kg of the resulting C18 internal olefin (g) were mixed to produce 15.0 kg of C16 / C18 internal olefin (mass ratio 79.4 / 20.6). The double bond distribution of the resulting internal olefin was 0.7% by mass in a C-1 position, 22.0% by mass in a C-2 position, 18.8% by mass in a C-3 position, 16 , 4 mass% in a C-4 position, 16.3 mass% in a C-5 position, 10.5 mass% in a C-6 position, 7.5 mass% in a C-7 position , 6.9% by mass in a C-8 position and 0.9% by mass in a C-9 position.
[086] A physical property of the internal olefin obtained by Production Examples A to K described above is shown in Table 1.
Table 1
Petition 870160043543, of 8/15/2016, p. 46/67
37/56
jjj2 E * S B LÍ £ CD with o - CMTf nCVJ OJ Φ ->| iB BX ELU □ _ oo o * - EM<0 eri in CM Φ _| íi LU D_ to co c - ojCDΌΪ r-- the QC * O4¾1 fX ELU D_ o with O —- C »JCD Tf<T> CO and " OiiLU CL <qco tT ci ra LA »IlÊ * E E K EUJ ü- <0CO o - OJ«Laughs hereCM Φ LU| íf LLI D_ Tf CO ΐ ^Q ft uo X E. UJ CL CO rtdog Φ 0£ *LU ü- COf i-* BX ELU D_<d * <s íLU CL <O lO <oQ Ίλ 8 QQ) Q ® Έ E 'Φ S ® O ç Ω. s Ή «ic ni Ο φ ** E õ ® o H o cn 4tj 5 ® S -o ^L Ti _ q> o, SJ t> 5 3 ra NZES, * cn fii S φ 'be φ Φ □ U OJ δ g S o ^w o * cn 1Ξ «N Cl o ΪΠ 3 Cl □ í T
(2) Production of an internal olefin sulfonate
Petition 870160043543, of 8/15/2016, p. 47/67
38/56
Production Example 1 [087] Using a thin-film sulfonation reactor having an outer jacket, the internal olefin sulfonation reaction having 16 carbon atoms (the content of an internal olefin where a double bond is present in a C position -2 is 16.5% by mass) obtained in Production Example A was carried out by passing through sulfur trioxide gas, while passing cooled water of 20 ° C through the outer jacket of the reactor. The molar ratio of SO3 / internal olefin for the sulfonation reaction was adjusted to 1.09. The resulting sulfonation product was added to an aqueous alkaline solution prepared with 1.5 times the molar amount of sodium hydroxide in relation to the theoretical acid value, followed by neutralization at 30 ° C for one hour with stirring. The resulting neutralized product was hydrolyzed by heating at 160 ° C for one hour in an autoclave, whereby a crude product of internal C16 sodium olefin sulfonate was obtained. Then, 300 g of the crude product were transferred to a separatory funnel, to which 300 ml of ethanol were added and then 300 ml of petroleum ether was added by operation, whereby oil-soluble impurities were removed by extraction. At this time, the inorganic compounds (mainly sodium sulfate compounds) that were precipitated at the oil-water interface by the addition of ethanol were also separated and removed from the aqueous phase by the oil-water separation operation. The above removal / extraction operation was repeated three times. Then, the side of the aqueous phase was evaporated to dryness, through which sodium C16 internal olefin sulfonate was obtained. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 81/19. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (less than GC detection limits), while the content of inorganic compounds in it was 1.3 % in large scale. In addition, the content of a
Petition 870160043543, of 8/15/2016, p. 48/67
39/56 internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 9.3% by weight.
Production Example 2 [088] An internal C18 sodium olefin sulfonate was obtained under the same conditions used in Production Example 1 from the internal olefin having 18 carbon atoms (the content of an internal olefin, where a double bond present in a C-2 position is 16.9% by mass) obtained in Production Example B.
[089] The mass ratio of the hydroxy form / olefin form to the internal sodium olefin sulfonate obtained was 80/20. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 1.7% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 9.6% by weight.
Production Example 3 [090] An internal C16 sodium olefin sulfonate was obtained under the same conditions used in Production Example 1 from the internal olefin having 16 carbon atoms (the content of an internal olefin, where a double bond present in a C-2 position is 30.4% by mass) obtained in Production Example C.
[091] The mass ratio of the hydroxy form / olefin form to the internal sodium olefin sulfonate obtained was 90/10. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 1.9% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 20.3% by weight.
Production Example 4 [092] An internal C18 sodium olefin sulfonate was obtained under the same conditions used in Production Example 1 from the internal olefin having 18 parts
Petition 870160043543, of 8/15/2016, p. 49/67
40/56 mos of carbon (the content of an internal olefin, where a double bond is present at a C-2 position is 31.3% by mass) obtained in Production Example D.
[093] The mass ratio of the hydroxy form / olefin form to the internal sodium olefin sulfonate obtained was 80/20. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 0.9% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 21.4% by weight.
Production Example 5 [094] Using a thin-film sulfonation reactor having an outer jacket, the sulfonation reaction of the internal olefins that have 18 carbon atoms (the content of an internal olefin, in which a double bond was presented in a position C-2 was 16.9% by mass) obtained in Production Example B was carried out by passing through sulfur trioxide gas, while passing cooled water of 20 ° C through the outer jacket of the reactor. The molar ratio of SOs / internal olefin for the sulfonation reaction was adjusted to 1.09. The resulting sulfonation product was transferred to a round bottom flask and aged by heating at 40 ° C for 30 minutes during stirring. Subsequently, the resulting product was added to an aqueous alkaline solution prepared with 1.5 times the molar amount of sodium hydroxide in relation to the theoretical acid value, followed by neutralization at 30 ° C for one hour with stirring. The resulting neutralized product was hydrolyzed by heating at 160 ° C for one hour in an autoclave, whereby a crude product of internal C18 sodium olefin sulfonate was obtained. Then, 300 g of the crude product was transferred to a separatory funnel, to which 300 ml of ethanol were added and then 300 ml of petroleum ether were added per operation. The extraction operation was performed three times. The aqueous phase was evaporated to dryness to obtain a C18 internal olefin sulfonate of
Petition 870160043543, of 8/15/2016, p. 50/67
41/56 sodium. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 57/43. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit), while the content of the inorganic compounds in it was 1.2% in large scale. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 9.6% by weight.
Production Example 6
Synthesis of C14 internal olefin sulfonate [095] A C14 sodium internal olefin sulfonate was obtained under the same conditions as Production Example 1 from the internal olefin having 14 carbon atoms (the content of an internal olefin, in which a double bond was presented in a C-2 position was, 31.8% by mass) obtained in Production Example E.
[096] The mass ratio of the hydroxy form / olefin form to the internal sodium olefin sulfonate obtained was 93/7. In addition, the content of the internal raw material olefin contained in the internal sodium olefin sulfonate was 0% by mass and that of the inorganic compounds in it was 0% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 21.7% by weight.
Production Example 7 [097] The composition obtained in Production Example 1 and the composition obtained in Production Example 2 were mixed in a mass ratio of 80:20 to obtain the internal olefin sulfonate composition 1.
Production Example 8 [098] The composition obtained in Production Example 1 and the composition obtained in Production Example 2 were mixed in a mass ratio of 90:10 to obtain the internal olefin sulfonate composition 2.
Petition 870160043543, of 8/15/2016, p. 51/67
42/56
Production Example 9 [099] The composition obtained in Production Example 1 and the composition obtained in Production Example 2 were mixed in a mass ratio of 75:25 to obtain the internal olefin sulfonate composition 3.
Production Example 10 [0100] The composition obtained in Production Example 6, the composition obtained in Production Example 1 and the composition obtained in Production Example 2 were mixed in a mass ratio of 50:40:10 to obtain the composition of internal olefin sulfonate 4.
Production Example 11 [0101] The composition obtained in Production Example 1 and the composition obtained in Production Example 5 were mixed in a mass ratio of 75:25 to obtain the internal olefin sulfonate composition 5.
Production Example 12 [0102] The composition obtained in Production Example 3 and the composition obtained in Production Example 4 were mixed in a mass ratio of 80:20 to obtain the internal olefin sulfonate composition 6.
Production Example 13 [0103] The C16 / 18 internal olefins (the content of internal olefin in which the double bonds are present at the C-2 position is 27.8% by mass) obtained in Production Example F were used as a material and a C16 / C18 internal olefin sulfonate sodium (composition of internal olefin sulfonate 7) was obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 86/14. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the compos
Petition 870160043543, of 8/15/2016, p. 52/67
43/56 inorganic products was 1.2% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 17.6% by weight.
Production Example 14 [0104] The composition obtained in Production Example 3 and the composition obtained in Production Example 4 were mixed in a mass ratio of 90:10 to obtain the internal olefin sulfonate composition 8.
Production Example 15 [0105] The composition obtained in Production Example 3 and the composition obtained in Production Example 4 were mixed in a mass ratio of 75:25 to obtain the internal olefin sulfonate composition 9.
Production Example 16 [0106] The composition obtained in Production Example 6, the composition obtained in Production Example 3 and the composition obtained in Production Example 4 were mixed in a mass ratio of 50:40:10 to obtain the composition of internal olefin sulfonate 10.
Production Example 17 [0107] The internal olefins C16 / 18 (the content of internal olefin in which the double bonds are present in the C-2 position is 45.3% by mass) obtained in Production Example G were used as a material and a C16 / C18 internal olefin sulfonate (composition of internal olefin sulfonate 11) was obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 92/8. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 0.3% by mass. In addition, the content of an olefin sulfonate
Petition 870160043543, of 8/15/2016, p. 53/67
44/56 internal, in which a sulfonate group is present in a C-2 position, was 25.2% by mass.
Production Example 18 [0108] The C16 / 18 internal olefins (the internal olefin content, where the double bonds are present at the C-2 position, is 34.8% by mass) obtained in Production Example H was used as a raw material and a C16 / C18 internal olefin sulfonate (composition of internal olefin sulfonate 12) were obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 93/7. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 0.3% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 21.1% by weight.
Production Example 19 [0109] The C16 / 18 internal olefins (the internal olefin content, where the double bonds are present at the C-2 position is 27.8% by mass) obtained in Production Example F were used as a raw material, and an internal olefin sulfonate C16 / C18 sodium (composition of internal olefin sulfonate 13) was obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 93/7. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was 0.2% by mass and that of the inorganic compounds was 0.0% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 17.8% by weight.
Petition 870160043543, of 8/15/2016, p. 54/67
45/56
Production Example 20 [0110] The C16 / 18 internal olefins (the internal olefin content, in which the double bonds are present at the C-2 position, is 30.1% by mass) obtained in Production Example I were used as a raw material and a C16 / C18 internal olefin sulfonate (composition of internal olefin sulfonate 14) was obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 93/7. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was 0.2% by mass and that of the inorganic compounds was 0.4% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 18.0% by weight.
Production Example 21 [0111] The C16 / 18 internal olefins (the internal olefin content, where the double bonds are present in the C-2 position, is 25.8% by mass) obtained in Production Example J were used as a raw material, and an internal C16 / C18 sodium olefin sulfonate (composition of internal olefin sulfonate 15) was obtained in the same manner as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) ) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 93/7. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was less than 100 ppm (below the GC detection limit) and that of the inorganic compounds was 0.8% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 16.7% by weight.
Production Example 22 [0112] C16 / 18 internal olefins (the content of internal olefin, where the bonds
Petition 870160043543, of 8/15/2016, p. 55/67
46/56 doubles are present in position C-2, it is 22.0% by mass) obtained in Production Example K were used as a raw material and an internal olefin sulfonate C16 / C18 of sodium (olefin sulfonate composition internal 16) was obtained by the same way as Production Example 1. The mass ratio of the hydroxy form (sodium hydroxyalkane sulfonate) / olefin form (sodium olefin sulfonate) in the internal sodium olefin sulfonate obtained was 93 / 7. In addition, the content of the internal olefin of raw material contained in the internal sodium olefin sulfonate obtained was 0.2% by mass and that of the inorganic compounds was 0.7% by mass. In addition, the content of an internal olefin sulfonate, in which a sulfonate group is present at a C-2 position, was 13.7% by weight.
[0113] A physical property of the internal olefin sulfonates obtained by Production Examples 1 to 6 is shown in Table 2 and a physical property of the internal olefin sulfonate compositions 1 to 16 obtained by Production Examples 7 to 22 is shown in Table 3.
Table 2
Petition 870160043543, of 8/15/2016, p. 56/67
47/56
I fLU CL Φ ll-PΦ fx K LLI CL • * r eqC3 D) O<N O O Φ tfli iLLI CL 1m iliu.iiLU LL CO Hi<£> 5 <O<3> O ΓΜ QJ «-- iE * È B X t-LU LL u α- <E =S Bx SLU LL it's the cq dog the CSIO00 CM £ Q O.O O O> G P-S BX t.LU □. 0) Q | íÈ Bx tf LU CL Ass Ô CQ Oo σ> OThe CM ANDO. Q.The QV σ> B <N £ l-x SLU LL ω mI £P-È BX tfLU CL co cnCD the CMOCO <3 O ANDQ. Q.O OVIiHLU LL u <° Ι-Ε *5 BX tLU LL «D L £ DCD OT1-CO cqD) ANDTheThethe oV cq íü c £ _u C a r _e 0> Ό JD 'ra c £ 3 ω The t «s í>3TJThe Cl0) TJthe CLAND0) x; LU QTJQc 1Ί3Q C -e ϊ δ. Φ ¢ 0 TJ. £ <n mThe JttE °O o311 φ Φ H <n ÜQ Φ £ Ό o fl] cn - üj ra o = δ O ^{- c} and ¹¹ <Ê o tfl (11 ra 5. □ í ra, çJ * oOfrogANDiX ‘OP JZa> T>frogISs O o * c <5i σQ. ra c σ IS c £DHEREOQ.3& Φ c ra cΦ Έfrogc L3J OOQ _Q frogsfrogANDΦ ΌP} g p Έfrog3 G £the Q ‘c tfljQ _ÇQ ΉQE Q <_)Φ ΠΦPG¢ 133 O o ™B Ξf £Frog£ra nj Ξ o Φ Ή ro o J> C & O fg Έ generates c P ^c E ia u = o □ Φ O ⁰¹ õ
Petition 870160043543, of 8/15/2016, p. 57/67
48/56 [0114] Table 3
8| you π £ r 5 "H to «ί - s> Os sSi04O O Η π s-8 “J ' ç _i § u ® CO O · - <N il CO iri M sσι O AND8V CO α β 8 f tiJJJ □. gS.:S ANDO · 3liUJ X 2 ce o - «to O 5 hello CM and> O O -£ 18- y! UJ ÍL · sQ «£ «£ 1t11 «Fi tfi o —- csl fv s to CM o the 3rd '1 r UJ ÍL · t r3 ftS Έ ώ i s ΪΟ ô - « «J π P5 σ> 04 ANDCLThe.8V fr O β Ϊ ftLU CL s.1 ’f φ uj11 w CO Cb i— PJ c3T- «S'w- m3 QOCJ Cf) m«7Γ4 And the8V O «1 f 1 h O£8 andI-S Ο Φf I § | ^ t11 ° 11 • -«11 to £" Oit í | § F3ii «íhUJ CL · ti Ϊ5- = & 8 "f-8 φt t £ 1 T d• R -IG. ! „LU □. â r3 <u15ê 3 ίΑ 05 φ ””I have you here POO OO-jCM And thethe oV ϊΜ ® S!li n The s-8 “8 ®f t s 8 I S * §iLU 0. §FΦo -RS. i ® o · jrhs S iSItUJ 0. s1'33 _o O ™ Q. £ 4 ã Ο Έ 'J 1 ® there β cr, it · f uj a_ £8 m18 φf i § S w £ «¢, £ 11S ώ £ s í ^w 5& 'O' S 'E -g ô Ώ g ItUJ CL · fi Γ3f = “ii «SHLU CL li “1 · =g1O-8S £-88 's laughUJ CL · 58 82 *lis IpUt li i 13; 1® i! c Cl ε s ®S S: S. “t £Φi í8l w jk’3HS 3ifi- fnj1Í2 eI I!3 σ g · §£18 «Φ1 Ί d s g* Y h_____2_S____ φ OJli 13 «Í
Petition 870160043543, of 8/15/2016, p. 58/67
49/56
HAIR ASSESSMENT [0115] A bundle of hair (hair of a Japanese person free of treatment, such as bleaching or hair dye; approximately 20 cm, 15 g) was cleaned with a simple shampoo shown below. Then, after applying a simple rinse shown in the table below, the hair bundle was rinsed with tap water to obtain a curl for evaluation.
[0116] Each of the internal olefin sulfonate compositions 1 to 16 obtained in Production Examples 7 to 22 was dissolved in exchange for ion exchange water to prepare an aqueous solution (13 wt.%) Of the internal olefin sulfonate composition. Using these aqueous solutions, five experts assessed their foaming ability, foam quality, foaming speed and foam dissipation property, according to the evaluation criteria and evaluation methods shown below (specifically, 1.0 g of each aqueous solution (13% by mass) prepared by using the internal olefin sulfonate compositions shown in Table 6 was applied to the bunch for evaluation and subjected to foam, cleaning and then rinsing).
[0117] In addition, in the condition that 0.05 ml of model tallow was applied to the hair, the durability of the foam in the presence of model tallow was assessed by washing it using 1.0 g of the aqueous solution (13% by mass) prepared using the internal olefin sulfonate compositions shown in Table 6. The model tallow was prepared by uniformly mixing 80/20% by weight of triolein / lanolin at 40 ° C.
[0118] The results are shown in Table 6. Table 7 also shows the evaluation results when using polyoxyethylene alkyl sulfate (AES), olefin α sulfonate (AOS) and secondary alkyl sulfonate (SAS), instead of above-mentioned internal olefin sulfonate composition.
Table 4
Petition 870160043543, of 8/15/2016, p. 59/67
50/56
Composition of simple shampoo
Component ________________________________________________ (%)
Sodium lauryl polyoxyethylene ether sulfate11.3 (42.0% in terms of EMAL E-27C (manufactured by Kao Corp .; 27% by weight of active component))
Coconut oil fatty acid N-methylethanolamide3,0 (AMINON C-11S (manufactured by Kao Corp.))
Citric acid0,2
Methylparaben0.3
Purified water ____________________________________________________ Balance
Total100.0
PRODUCTION OF SIMPLE SHAMPOO [0119] The components were placed in a beaker, heated to 80 ° C and then mixed. After confirmation of uniform dissolution, the mixture was cooled to obtain a simple shampoo.
Table 5
Composition of simple rinse (Component) ___________________________________________________ (%)
Octadecyloxypropyl trimethyl ammonium chloride3.0 (6.7% in terms of QUARTAMIN E-80K (manufactured by Kao Corp .; 45% by weight of active component))
Stearyl alcohol 6.0 (KALCOL 8098 (manufactured by Kao Corp.))
Methylparaben0.3
Purified Water __________________________________________________ Balance
Total100.0
SIMPLE RINSE PRODUCTION
Petition 870160043543, of 8/15/2016, p. 60/67
51/56 [0120] Octadecyloxypropyl trimethyl ammonium chloride and stearyl alcohol were placed in a beaker (A) and melted by heating to 80 ° C. Purified water and methylparaben were placed in another beaker (B) and heated to 80 ° C with stirring. After confirmation of uniform dissolution, the solution mixed in the beaker (A) was added to the beaker (B) with stirring at 80 ° C and emulsified for 30 minutes. The heating was finished, and it was cooled to room temperature to obtain a simple rinse.
EVALUATION CRITERIA AND EVALUATION METHODS
Foaming capacity [0121] 5: Foaming properties were very satisfactory [0122] 4: Foaming properties were satisfactory [0123] 3: Usual foaming capacity (equivalent to Comparative Example 1: AES) [0124] 2: Foaming properties were deficient [0125] 1: Foaming properties were very deficient to clean hair
Foaming speed [0126] 5: Foam was very fast and facilitated cleaning [0127] 4: Foam was fast [0128] 3: Usual (equivalent to Comparative Example 1: AES) [0129] 2: Foam was slow [ 0130] 1: Foam was too slow
Foam quality [0131] 5: Foam quality was creamy and very satisfying [0132] 4: Foam quality was slightly creamy and satisfactory [0133] 3: Foam quality was usual (equivalent to Comparative Example 1: AES)
Petition 870160043543, of 8/15/2016, p. 61/67
52/56 [0134] 2: Foam quality was slightly sparkling and deficient [0135] 1: Foam quality was sparkling and very deficient and prevented cleaning
Foam dissipation property [0136] 5: Foam was very quickly dissipated and easily rinsed [0137] 4: Foam was quickly dissipated [0138] 3: Usual (equivalent to Comparative Example 1: AES) [0139] 2: Foam was slow dissipated [0140] 1: Foam was very slowly dissipated and hardly rinsed
Foam durability in the presence of tallow model [0141] 5: Foam durability was very satisfactory (not feeling a decrease in foam volume during washing) [0142] 4: Foam durability was satisfactory (less decrease in foam volume) [0143] 3: Usual foam durability (equivalent to Comparative Example 1: AES) [0144] 2: Foam durability was deficient (noticeable decrease in foam volume) [0145] 1: Foam was not maintained (defoaming was found during the washing)
HAND WASH ASSESSMENT [0146] Each of the internal olefin sulfonate compositions 1 to 16 obtained in Production Examples 7 to 22 was dissolved in ion exchange water to prepare an aqueous solution (13% by mass) of the sulfonate composition of internal olefin. Using these aqueous solutions, five experts washed their hands and assessed the foaming ability, foam quality and foam dissipation property, according to the following evaluation criteria and
Petition 870160043543, of 8/15/2016, p. 62/67
53/56 evaluation method (specifically, 1.0 g of the aqueous solution (13% by mass) prepared using the internal olefin sulfonate compositions shown in Table 6 applied to the hands and subjected to foam, cleaning and rinsing).
[0147] In addition, in the condition that 0.05 ml of model tallow was applied to the hand, the durability of the foam in the presence of model tallow was assessed by washing it using 1.0 g of aqueous solution (13% by weight) ) prepared using the internal olefin sulfonate compositions shown in Table 6. The model tallow was prepared by uniformly mixing 80/20% by weight of triolein / lanolin at 40 ° C.
[0148] The results are shown in Table 6. Table 7 also shows the evaluation results when using polyoxyethylene alkyl sulfate (AES), olefin α sulfonate (AOS) and secondary alkyl sulfonate (SAS), instead of above-mentioned internal olefin sulfonate composition.
FOAM VOLUME TEST [0149] A curl treated in the same way for hair evaluation was used. Foam obtained by foaming in the same form as above was placed in a graduated cylinder of 5 cm in diameter made of glass and the volume of the foam was measured. This operation was repeated three times and an average (rounded to the nearest whole number) was defined as the volume (mL) of foam. In addition, a bunch to which the model tallow (0.05 ml) is applied was used and the volume (ml) of foam was measured in the same way as for hair evaluation. The measured value was considered as the volume of foam (mL) in the presence of model tallow.
Table 6
Petition 870160043543, of 8/15/2016, p. 63/67
54/56
¢ 0 <u Cl Ό ~ fl ”1 s sHELLO O O s.CO <37 d CM CM CMGJ O · 0. to 0 _L · '0: —c -Z:i: rt * 4 cm; 0 d: d O d O (Mud.cd 0 ιΛ £ 5 ® hLU Cl · 4A O- CM ώ o ü “ s <n TÓ QCLQIN ISELQ.§ 00Hi slg Φ 0 0: 0 d M ² 00 " CD hey0ud.cd »£ Ílü a. s- S O | O The cr> CO Oó CM Ô 3di 8 0 d G30 iri d and © O: j £> «5 0. ·: CO:>; CO _: s jl © ϊíles- S 8"8Ο II O s CO COin cM0 Φ d o ^: ££ '0 K »': Ξ2: co 0 0I 0 0 d O-ep 0CN It slο II 8 s CO xr AND8 d 0CD 0 CM ed iM d CO 8 ca d 0 0 d 3 - Φ tPI LU Cl £ SÈ 1The li 8 03 LT> LíS ¢ 4 LfS ANDαsV 00d 0 hello O The d Φ d d QLíl 00 CM d 0 d tfM d O H1 UJ a «O O5S- Nf ââ L> ii s im07m8 CM CM andat m d 0 s0 3 CM 00© d cM CM 3 cn 0It - t-jE £ l · LT *2 7 O iq cmin60 <£>0 C ©0 £ &8 O eq "Π 0 ed 3 d0 en 0CD © d 0 d 3 w 41 Ji| §11 2 * 8 07 « The CM The co And the.sV QC CM 0 0 cd 5 CD dO d d CM r- tt LO ”a il ·tl Α 7 . to « <C> «Μ ANDú. Q.OOV CM O the CO 0 0 CD 3 inO ID d © d 0 d <q m and-Is O5 the cd CM00Q <r> the CM 00 £ Cl8 ΙΛ 8 -Hn S tU LT>«- Cm2 ΪΓ Q O ΙΛ cmu HI 00 £O.O « 3 7H h i cí5S- m O II The m the CMCO HI 00 And the.8V O CM 0<M CM 0 CM 00 0 The d OCM 0CM n 8 -ofi h s s i>. 57 8 Q CMGJ you s 0ttí It's gQCM 00 eqd d Ç 0 d The d CM cd d cm The '&H ώ t "it's theÕ Q O OCMQ ao CO hi 00 ANDQ.α<5O CO 0 0 Q J CM 0d 0 0 © d 0 CM Φ d - ,H s § è sΟ II 8 CD CMx O ΪΧ3 Hi 00 And the.the oI ^s 0 0 cq f 0CM CM CM 0 dφ © 0 g 0 d 0 d internal olefin phonate 1 o ã _w 8 f ctj - 13 nj 8 Ί S 'o ΦΦ âIs £E g Φ E ΦΦ the lfTO çlÍS g i § § I TO ^ ΦΦTO f £ΦΦ çjS Φ en v> _m E 3 <í and 8 ·; f S £ Sí õ CE ~ Φ ê 8 <0 gg Ê R «8i P = ô E Φf «J i H« £The.S Φ i | The!«J olaugh flj Eflj fO3T9i B'SiBtj! 1P &' s0Is£ 8 gΦ 8g.3 AND»Φ SΦ E ΦAND3J Ç£ $Φ£ gΛΦΦ 3-φ£fOgThe-Φ _φΦAND_O Π5iQ WS *1 § £ SΦ Π5Φ φ 3 ¹ o S g 1 0 <J sf φ -3 flj -S Φ · a> S 8 o. CS 80r3ΦΦ13 ΆΦ Φ0£ 8.sΦΦ13 IS8 SΦI3 I σ il sl tu ΛΤ Ό < l · Φ 4 H = i a ã w Φ i -8 O Φ n> O J | © 1JM <£ - yes ^s I ^s - AND£ Only the « ⁸ si Ξ CT g | S Φ i | σ s1 = 3 ç5 ís HF ^- Q £ ! UANDΦ g’.a íu E ã E 3 £ -SLlI ANDLU TS LU€ITHE í IG8 S r -o
Petition 870160043543, of 8/15/2016, p. 64/67
55/56
Table 7
CO to * ω< CQ O£ 3 poop 2.8 J OJ = Ί ^- 4.0 2.0 cqCM m * (Λ O< 5poo 3.8 * OJ 3.0 CN Q CM M * ω LU < 3.0 05 3.0 0 ¹ 0 poop poo 3.0 65 3.0 0poop 0 ró 3.0 Comparative Reference Examples Foaming capacity ¹ Foam volume Foam speed cu ECl ίΛ ΦΦΌThe ‘KU g. dogTOΦ ΌΦΌΦ c01_ 1 Foam quality Foam durability in the presence of ______de .seho. model Volume of foam in the presence ________ of tallow model______________ Foaming capacity Foam dissipation property (The ES'(O '75O 4<TJçΦ¢ 0£Q_¢ 0çANDQ_Φ03 Ç s il d 41 Hair Evaluation Hand wash assessment evaluation results
* 4: Roloxyethylene sodium alkyl sulfate * CAES), manufactured by Kao Corp., EMAL 27OS 0 Active component: 70%) * 5: Sodium α-olefin sulfate (AOS), manufactured by non uorp., LIPOLAN LB -440 (Active component 2 36%) * 6: Secondary sodium alkyl sulfonate (SAS), 1 manufactured by LANXESS KK, Mersolat H95 G Active component :: 95%)
INDUSTRIAL APPLICABILITY [0150] The internal olefin sulfonate composition of the present invention exercises
Petition 870160043543, of 8/15/2016, p. 65/67
56/56 satisfactory foaming capacity together with satisfactory foam quality, foaming speed, foam durability in the presence of model tallow and high-level foam dissipation property. Thus, the internal olefin sulfonate composition of the present invention can be used appropriately in the fields of household cleaning agents, such as hair shampoos, body cleaners, laundry detergents, kitchen detergents and residential detergents, and is also suitable for cosmetic emulsifiers, industrial emulsifiers, industrial cleaning agents or the like.

权利要求:
Claims (11)
[1]
1. Composition of internal olefin sulfonate CHARACTERIZED by the fact that it comprises (A) an internal olefin sulfonate having 16 carbon atoms and (B) an internal olefin sulfonate having 18 carbon atoms, in which a ratio of the mass content (A / B) from component (A) to component (B) is 75/25 to 90/10, and in which a mass ratio (hydroxy form / olefin form) to a content of a hydroxy form in the internal olefin sulfonate of component (A) and component (B) for an olefin form content in the internal olefin sulfonate of component (A) and component (B) is 75/25 to 100/0.
[2]
2. Composition of internal olefin sulfonate, according to claim 1, CHARACTERIZED by the fact that a total content of component (A) and component (B) in the internal olefin sulfonate is 50 to 100% by weight.
[3]
3. Internal olefin sulfonate composition according to claim 1 or 2, CHARACTERIZED by the fact that an internal olefin sulfonate content, in which a sulfonate group is present at a C-2 position in the internal olefin sulfonate component (A) and component (B), is 28% by weight or less.
[4]
4. Internal olefin sulfonate composition according to claim 1 or 2, CHARACTERIZED by the fact that an internal olefin sulfonate content, in which a sulfonate group is present at a C-2 position in the internal olefin sulfonate component (A) and component (B), is less than 20% by weight.
[5]
5. Internal olefin sulfonate composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that an internal olefin raw material content in the internal olefin sulfonate composition is less than 5% by mass regarding the amount of internal olefin sulfonates.
[6]
6. Composition of internal olefin sulfonate, according to any one
Petition 870190069029, of 7/22/2019, p. 11/13
2/2 of claims 1 to 5, CHARACTERIZED by the fact that the content of inorganic compounds in the composition of internal olefin sulfonate is less than 7.5% by weight with respect to the quantity of the internal olefin sulfonates.
[7]
7. Internal olefin sulfonate composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that it is obtained by sulfonating a composition of the internal olefin raw material containing an internal olefin raw material, followed by neutralization and then hydrolysis, a content of the internal olefin raw material, in which a double bond is present at a C-2 position, being 48% by weight or less.
[8]
8. Internal olefin sulfonate composition according to any one of claims 1 to 6, CHARACTERIZED by the fact that it is obtained by sulfonating the composition of the internal olefin raw material containing the internal olefin raw material, followed by neutralization and then hydrolysis, a content of the internal olefin raw material, in which a double bond is present at a C-2 position, being less than 20% by weight.
[9]
9. Cleaning composition CHARACTERIZED by the fact that it comprises the composition of internal olefin sulfonate as defined in any one of claims 1 to 8.
[10]
10. Cleaning composition according to claim 9, CHARACTERIZED by the fact that an internal olefin sulfonate content is 0.1 to 80% by weight.
[11]
Cleaning composition according to claim 9 or 10, CHARACTERIZED by the fact that it comprises one or more selected from an alkyl sulfate and a polyoxyalkylene alkyl sulfate.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112015004920B1|2020-03-03|INTERNAL OLEFINE SULPHONATE COMPOSITION AND CLEANING COMPOSITION CONTAINING THE SAME

---

JP6215629B2|2017-10-18|Internal olefin sulfonate composition and detergent composition containing the same

---

EP2899257B1|2018-05-30|Internal olefin sulfonate composition and detergent composition containing same

---

US9877907B2|2018-01-30|Internal olefin sulfonate composition

---

JP6542935B2|2019-07-10|Internal olefin sulfonate composition

---

US9861566B2|2018-01-09|Internal olefin sulfonate composition

---

US20140080751A1|2014-03-20|Internal olefinic sulfonate composition and cleansing composition containing the same

---

US9861567B2|2018-01-09|Internal olefin sulfonate composition

同族专利:

---

公开号 | 公开日

---

IN2015DN00103A|2015-05-29|

---

KR20150058170A|2015-05-28|

---

US10201488B2|2019-02-12|

---

CN104661637A|2015-05-27|

---

WO2014046301A2|2014-03-27|

---

CN108498361B|2021-10-12|

---

JP2015028123A|2015-02-12|

---

TWI600452B|2017-10-01|

---

TW201417857A|2014-05-16|

---

JP6439023B2|2018-12-19|

---

KR101992515B1|2019-06-24|

---

EP2897575A2|2015-07-29|

---

US20170281498A1|2017-10-05|

---

EP2897575B1|2020-05-06|

---

TW201737963A|2017-11-01|

---

CN104661637B|2020-06-19|

---

US9713584B2|2017-07-25|

---

TWI666038B|2019-07-21|

---

BR112015004920A2|2017-07-04|

---

JP6224390B2|2017-11-01|

---

CN108498361A|2018-09-07|

---

EP3685817A1|2020-07-29|

---

JP2018009189A|2018-01-18|

---

WO2014046301A3|2014-05-30|

---

US20150202134A1|2015-07-23|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3346629A|1963-08-15|1967-10-10|Monsanto Co|Process for preparing beta-ethylenically unsaturated organic sulfonates|

---

US3332880A|1965-01-04|1967-07-25|Procter & Gamble|Detergent composition|

---

ZA672362B|1965-08-04|

---

US3332828A|1965-12-28|1967-07-25|Monsanto Co|Monofilament ribbon pile product|

---

US3332878A|1966-12-05|1967-07-25|Procter & Gamble|Detergent composition having synergistic sudsing properties containing amides and sulfonate-containing detergents|

---

US3708437A|1969-12-04|1973-01-02|Chevron Res|2-olefin sulfonate for liquid detergents|

---

US3808157A|1970-06-10|1974-04-30|Ethyl Corp|Detergent composition containing a mixture of vinyl,vinylidene and internal olefin sulfonates|

---

JPS4978706A|1972-11-27|1974-07-30|

---

JPS5413242B2|1975-03-20|1979-05-29|

---

JPS5412485B2|1975-09-30|1979-05-23|

---

JPS5849595B2|1977-04-15|1983-11-05|Lion Corp|

---

JPS609695B2|1978-04-12|1985-03-12|Lion Corp|

---

JPS6145963B2|1978-09-21|1986-10-11|Lion Corp|

---

JPS5556196A|1978-10-20|1980-04-24|Lion Fat Oil Co Ltd|Liquid detergent composition|

---

US4280177A|1979-06-29|1981-07-21|International Business Machines Corporation|Implicit address structure and method for accessing an associative memory device|

---

JPS56167799A|1980-05-29|1981-12-23|Lion Corp|Liquid shampoo composition|

---

JPS6145964B2|1981-06-30|1986-10-11|Lion Corp|

---

US4597879A|1982-01-28|1986-07-01|Lion Corporation|Micellar slug for oil recovery|

---

JPH0157235B2|1982-01-28|1989-12-05|Lion Corp|

---

JPH0257598B2|1982-08-10|1990-12-05|Lion Corp|

---

JPH035368B2|1983-05-27|1991-01-25|Lion Corp|

---

JPS59222466A|1983-05-31|1984-12-14|Lion Corp|Sulfonation of olefin|

---

DE3416472A1|1984-05-04|1985-11-07|Hoechst Ag, 6230 Frankfurt|DETERGENT CONTAINING SOFTENER|

---

JPH0443904B2|1984-12-06|1992-07-20|Lion Corp|

---

JPS61247799A|1985-04-26|1986-11-05|Lion Corp|High concentrated surfactant slurry|

---

JPH01151510A|1987-12-09|1989-06-14|Lion Corp|Detergent composition|

---

JP2625150B2|1988-04-21|1997-07-02|ライオン株式会社|Manufacturing method of inner olefin sulfonate|

---

US4852653A|1988-07-06|1989-08-01|Shell Oil Company|Method to obtain rapid build-up of pressure in a steam foam process|

---

GB8817293D0|1988-07-20|1988-08-24|Shell Int Research|Process for preparation of internal olefin sulphonates|

---

GB8900023D0|1989-01-03|1989-03-01|Shell Int Research|Detergent composition|

---

US5580494A|1989-06-21|1996-12-03|Colgate-Palmolive Company|Hair conditioning shampoo containing high charge density polymers|

---

WO1997014396A1|1995-10-16|1997-04-24|The Procter & Gamble Company|Conditioning shampoo compositions|

---

FR2780278B1|1998-06-24|2001-01-19|Oreal|CONDITIONING AND DETERGENT COMPOSITION AND USE|

---

DE19845456A1|1998-10-02|2000-04-06|Cognis Deutschland Gmbh|Syndet bar soaps|

---

DE19911040A1|1999-03-12|2000-09-21|Cognis Deutschland Gmbh|Surfactant granules|

---

US6403654B1|2000-04-13|2002-06-11|Mariana De Oliveira|Compositions for and method of treatment for psoriasis|

---

US6184190B1|2000-06-08|2001-02-06|Colgate-Palmolive Co.|Aqueous solution of an alpha sulfonate surfactant comprising 1,3-bis -5, 5-dimethylimidazolidine-2, 4 dione|

---

DE10105139A1|2001-02-06|2002-08-22|Wella Ag|Electrically conductive polymers in cosmetic products|

---

JP2003018312A|2001-07-04|2003-01-17|Hitachi Kokusai Electric Inc|Remote monitor system and communication equipment to be remotely monitored|

---

JP2003081935A|2001-09-10|2003-03-19|Lion Corp|Internal olefin sulfonate and detergent composition including the same|

---

JP2003183152A|2001-12-21|2003-07-03|Kanebo Ltd|Creamy cleansing preparation for skin|

---

CN1782055A|2002-09-13|2006-06-07|株式会社日本触媒|Liquid detergent builder and liquid detergent containing the same|

---

GB0313998D0|2003-06-17|2003-07-23|Cambridge Advanced Tech|Plant limit dextrinase inhibitor|

---

EP1639016B1|2003-06-17|2011-03-09|Union Carbide Chemicals & Plastics Technology LLC|Cellulose ethers|

---

JP2007015940A|2005-07-05|2007-01-25|Nippon Shokubai Co Ltd|Shampoo composition|

---

SG185292A1|2007-10-26|2012-11-29|Chevron Oronite Co|Isomerized alpha olefin sulfonate and method of making the same|

---

JP5210693B2|2008-04-11|2013-06-12|持田製薬株式会社|Enzyme cleansing powder|

---

US8097574B2|2009-08-14|2012-01-17|The Gillette Company|Personal cleansing compositions comprising a bacterial cellulose network and cationic polymer|

---

WO2011044305A1|2009-10-07|2011-04-14|The Procter & Gamble Company|Detergent composition|

---

MX2012005154A|2009-11-03|2012-09-12|Stepan Co|Sulfomethylsuccinates, process for making same and compositions containing same.|

---

US8318143B2|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|

---

JP5911240B2|2010-10-04|2016-04-27|キヤノン株式会社|Porous glass, manufacturing method thereof, optical member, and imaging apparatus|

---

CN102504791A|2011-11-10|2012-06-20|东北石油大学|C18 olefin sulfonate surfactant and preparation method thereof|

---

AR090481A1|2012-03-26|2014-11-12|Univ Texas|USE OF A SOFT ALKAL AGENT IN THE RECOVERY OF PETROLEUM|

---

JP6243673B2|2012-09-20|2017-12-06|花王株式会社|Internal olefin sulfonate composition and detergent composition containing the same|

---

JP6235844B2|2012-09-20|2017-11-22|花王株式会社|Cleaning composition for skin or hair|

---

JP6224390B2|2012-09-20|2017-11-01|花王株式会社|Internal olefin sulfonate composition and detergent composition containing the same|

---

JP6215629B2|2012-09-20|2017-10-18|花王株式会社|Internal olefin sulfonate composition and detergent composition containing the same|

---

JP6300477B2|2012-09-20|2018-03-28|花王株式会社|Cleaning composition for skin or hair|

---

US8940673B2|2012-09-20|2015-01-27|Kao Corporation|Skin cleansing composition|

---

US20140080746A1|2012-09-20|2014-03-20|Kao Corporation|Cleansing composition for skin or hair|

---

US20140079660A1|2012-09-20|2014-03-20|Kao Corporation|Cleansing composition for skin or hair|

---

US20140079658A1|2012-09-20|2014-03-20|Kao Corporation|Aqueous hair cleansing agent|JP6224390B2|2012-09-20|2017-11-01|花王株式会社|Internal olefin sulfonate composition and detergent composition containing the same|

---

JP6235843B2|2012-09-20|2017-11-22|花王株式会社|Cleaning composition for skin or hair|

---

JP6300477B2|2012-09-20|2018-03-28|花王株式会社|Cleaning composition for skin or hair|

---

JP6243672B2|2012-09-20|2017-12-06|花王株式会社|Cleaning composition for skin or hair|

---

JP6235844B2|2012-09-20|2017-11-22|花王株式会社|Cleaning composition for skin or hair|

---

EP2952566B1|2013-02-01|2022-01-05|Kao Corporation|Internal olefin sulfonate composition|

---

US9861566B2|2013-02-01|2018-01-09|Kao Corporation|Internal olefin sulfonate composition|

---

CN108078799B|2013-02-01|2021-07-23|花王株式会社|Internal olefin sulfonate compositions|

---

EP2957625B1|2013-02-13|2018-07-18|Kao Corporation|Internal olefin sulfonate composition|

---

FR3018684B1|2014-03-19|2017-05-12|Oreal|COSMETIC COMPOSITION COMPRISING BENEFICIAL AGENTS FOR KERATINIC MATERIALS, AND A MIXTURE OF OLEFIN SULFONATE DERIVATIVES, AND COSMETIC TREATMENT PROCESS|

---

JP2015178467A|2014-03-19|2015-10-08|ロレアル|Foamable composition including internal olefin sulfonate and one foam formation promotor or foam formation enhancer|

---

JP6471013B2|2015-03-25|2019-02-13|花王株式会社|Anionic surfactant composition for emulsion polymerization|

---

JP6517090B2|2015-06-18|2019-05-22|花王株式会社|Pesticide enhancer composition|

---

CN105273639A|2015-11-14|2016-01-27|华玉叶|Tire brightener|

---

CN108368455B|2015-12-10|2020-11-10|花王株式会社|Surfactant composition|

---

WO2017098639A1|2015-12-10|2017-06-15|花王株式会社|Surfactant composition|

---

EP3388505B1|2015-12-10|2020-04-01|Kao Corporation|Surfactant composition|

---

RU2747642C2|2016-05-31|2021-05-11|Као Корпорейшн|Detergent composition for textile products|

---

RU2744265C2|2016-05-31|2021-03-04|Као Корпорейшн|Liquid detergent composition for textile products|

---

RU2737429C2|2016-05-31|2020-11-30|Као Корпорейшн|Liquid detergent composition for textile products|

---

WO2017209119A1|2016-05-31|2017-12-07|花王株式会社|Method for cleaning clothing|

---

EP3467088B1|2016-05-31|2020-07-29|Kao Corporation|Liquid detergent composition|

---

US10660837B2|2016-08-31|2020-05-26|Kao Corporation|Oral composition and oral plaque dispersion agent|

---

WO2018070516A1|2016-10-14|2018-04-19|花王株式会社|Fiber product finishing agent composition|

---

CN106711503A|2016-12-19|2017-05-24|西南石油大学|Single-ion gel polymer electrolyte and preparation method thereof|

---

JP2018177779A|2017-04-10|2018-11-15|花王株式会社|Skin cleanser composition|

---

CN110520102A|2017-04-10|2019-11-29|花王株式会社|Composition of skin cleanser|

---

WO2018190302A1|2017-04-10|2018-10-18|花王株式会社|Keratin plug removal method|

---

KR20190131512A|2017-04-10|2019-11-26|카오카부시키가이샤|Skin cleanser composition|

---

EP3610849A4|2017-04-10|2021-01-13|Kao Corporation|Keratin plug removal method|

---

EP3610851B1|2017-04-10|2022-02-16|Kao Corporation|Skin cleanser composition|

---

CN107177426A|2017-05-26|2017-09-19|石海光|A kind of low bubble laundry care agent|

---

CN110832059B|2017-07-14|2021-08-31|花王株式会社|Method for cleaning hard article|

---

US20200354650A1|2017-12-06|2020-11-12|Kao Corporation|Detergent composition for textile products|

---

CN111448348A|2017-12-06|2020-07-24|花王株式会社|Fabric treatment composition|

---

US20200369985A1|2017-12-06|2020-11-26|Kao Corporation|Composition|

---

JP6956000B2|2017-12-27|2021-10-27|花王株式会社|Oral composition|

法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

---

2019-05-21| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

---

2020-01-28| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-03-03| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

JP2012-207570|2012-09-20|

---

JP2012207570|2012-09-20|

---

JP2013-132314|2013-06-25|

---

JP2013132314|2013-06-25|

---

PCT/JP2013/076174|WO2014046301A2|2012-09-20|2013-09-19|Internal olefin sulfonate composition and cleansing composition containing same|

---