WO2017098637A1 - 界面活性剤組成物 - Google Patents
界面活性剤組成物 Download PDFInfo
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- WO2017098637A1 WO2017098637A1 PCT/JP2015/084686 JP2015084686W WO2017098637A1 WO 2017098637 A1 WO2017098637 A1 WO 2017098637A1 JP 2015084686 W JP2015084686 W JP 2015084686W WO 2017098637 A1 WO2017098637 A1 WO 2017098637A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 144
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 124
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 157
- -1 olefin sulfonates Chemical class 0.000 claims abstract description 91
- 239000004711 α-olefin Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims description 82
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 27
- 239000003599 detergent Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 14
- 239000012459 cleaning agent Substances 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 8
- 125000001174 sulfone group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 38
- 150000003871 sulfonates Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 29
- 238000004519 manufacturing process Methods 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 239000012467 final product Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005187 foaming Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 150000002484 inorganic compounds Chemical class 0.000 description 8
- 229910010272 inorganic material Inorganic materials 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 239000002453 shampoo Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 102220465933 Beta-1,3-glucuronyltransferase LARGE2_R15A_mutation Human genes 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 101100256077 Caenorhabditis elegans aos-1 gene Proteins 0.000 description 2
- 229920002907 Guar gum Polymers 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-NJFSPNSNSA-N Carbon-14 Chemical compound [14C] OKTJSMMVPCPJKN-NJFSPNSNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102220549062 Low molecular weight phosphotyrosine protein phosphatase_C13S_mutation Human genes 0.000 description 1
- 241000282372 Panthera onca Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
- A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/596—Mixtures of surface active compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to a surfactant composition containing an internal olefin sulfonate at a high concentration.
- An internal olefin sulfonate which is a kind of anionic surfactant, is generally obtained by reacting an internal olefin with sulfur trioxide gas for sulfonation, neutralizing the resulting sulfonic acid, and further hydrolyzing it.
- an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms are known to be excellent in foaming properties and detergency, and have been conventionally used in various cleaning agents.
- an internal olefin sulfonate has an increased viscosity as its concentration is increased, and there is a possibility that the handleability is remarkably lowered.
- the internal olefin sulfone is as much as possible while ensuring the desired effect. It is desirable to increase the concentration of the acid salt.
- Patent Document 1 discloses that an olefin sulfonate containing 50% by weight or more of an internal olefin sulfonate is 55 to 75% by weight, a specific hydrocarbon such as an olefin is 5 to 40% by weight, and water. Has been disclosed, and attempts have been made to lower the viscosity of the resulting slurry.
- Patent Document 1 JP 59-27995 A
- the present invention includes the following components (A), (B), and (C): (A) Internal olefin sulfonate having 16 to 18 carbon atoms, 45.0 mass% to 70.0 mass%, (B) Alpha olefin sulfonate having 12 or more and 14 or less carbon atoms 0.5% by mass or more and 25.0% by mass or less, and (C) containing water, and the total content of component (A) and component (B) It is related with surfactant composition whose quantity is 66.0 mass% or more and 71.0 mass% or less.
- an internal olefin sulfonate having 16 to 18 carbon atoms has a high content
- an alpha olefin sulfonate having 12 to 14 carbon atoms is added. It has been found that a surfactant composition capable of ensuring high fluidity and excellent storage stability can be obtained by using these in a specific amount together and setting them to a specific total content.
- the surfactant composition of the present invention high fluidity is achieved while containing a high concentration of an internal olefin sulfonate having 16 to 18 carbon atoms that can exhibit excellent foaming and cleaning properties. And exhibit excellent storage stability in a wide temperature range. Therefore, as a base for final products of various cleaning agents such as clothing cleaners, dish cleaners, hair cleaners, body cleaners, precision parts cleaners, and hard surface cleaners in a wide range of fields. It is a highly useful surfactant composition that can be used effectively.
- the surfactant composition of the present invention comprises the following components (A), (B), and (C): (A) Internal olefin sulfonate having 16 to 18 carbon atoms, 45.0 mass% to 70.0 mass%, (B) Alpha olefin sulfonate having 12 or more and 14 or less carbon atoms 0.5% by mass or more and 25.0% by mass or less, and (C) containing water, and the total content of component (A) and component (B) The amount is 66.0 mass% or more and 71.0 mass% or less.
- the surfactant composition of the present invention exhibits good fluidity and storage stability.
- a composition containing a high concentration of an internal olefin sulfonate having 16 to 18 carbon atoms as the component (A) there are two phases of micelle phase and lamellar phase in the system, and the phase difference is caused by the difference in specific gravity between them.
- the component (B) contains a specific amount of an alpha olefin sulfonate having a short carbon number of 12 or more and 14 or less, thereby reducing or eliminating the micelle phase. It is considered that phase separation is effectively suppressed.
- the alpha olefin sulfonate having 16 to 18 carbon atoms contained in the internal olefin sulfonate having 16 to 18 carbon atoms of the component (A) can be a precipitate. It is considered that the alpha olefin sulfonate having 12 to 14 carbon atoms improves the solubility and effectively suppresses the formation of precipitates. Furthermore, the micelle phase is reduced or disappeared, and a mixed lamellar phase containing such a component (B) is formed.
- the surfactant composition of the present invention is an internal olefin sulfonate having 16 to 18 carbon atoms (hereinafter referred to as “component”) from the viewpoint of excellent foamability and detergency in a final product such as a detergent using such a composition. (Also referred to as (A)) in an amount of 45.0 mass% to 70.0 mass%.
- the internal olefin sulfonate is obtained by sulfonating, neutralizing and hydrolyzing the raw material internal olefin having 16 to 18 carbon atoms (olefin having a double bond inside the olefin chain). Sulfonate.
- Such internal olefin includes a case where a trace amount of a so-called alpha olefin (hereinafter also referred to as ⁇ -olefin) in which the position of the double bond is located at the 1st position of the carbon chain is included.
- the product obtained is mainly a mixture of these, part of which is a hydroxyalkane sulfonate having a hydroxy group at the end of the carbon chain, or an olefin having a double bond at the end of the carbon chain.
- a sulfonate may be contained in a trace amount.
- each of these products and a mixture thereof are collectively referred to as an internal olefin sulfonate (component (A)).
- hydroxyalkane sulfonate is referred to as a hydroxy form of internal olefin sulfonate (hereinafter also referred to as HAS), and the olefin sulfonate is referred to as an olefin form of internal olefin sulfonate (hereinafter also referred to as IOS).
- HAS internal olefin sulfonate
- IOS olefin form of internal olefin sulfonate
- the carbon number of the internal olefin sulfonate of component (A) is 16 or more from the viewpoint of having good foaming properties, detergency and rinsing properties. Moreover, carbon number of the internal olefin sulfonate of a component (A) is 18 or less from a viewpoint of expressing fluidity
- component (A) In the case where the content of the internal olefin sulfonate having 16 carbon atoms of component (A) and the internal olefin sulfonate having 18 carbon atoms are mixed and used, the content of internal olefin sulfonate having 16 carbon atoms in component (A) is used.
- the mass ratio between the amount and the content of the internal olefin sulfonate having 18 carbon atoms has good foaming properties and detergency, From the viewpoint of rinsing properties, it is preferably 100/0 to 40/60, more preferably 95/5 to 50/50, and still more preferably 90/10 to 70/30.
- the mass ratio can be measured by a high performance liquid chromatography mass spectrometer (hereinafter abbreviated as HPLC-MS).
- an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms are separated from the component (A) or the resulting surfactant composition by HPLC, and each is subjected to MS.
- the mass ratio can be determined from the HPLC-MS peak area.
- Examples of the salt of the internal olefin sulfonate include alkali metal salts, alkaline earth metal (1/2 atom) salts, ammonium salts, and organic ammonium salts.
- Examples of the alkali metal salt include Na salt and K salt.
- the sulfonic acid group of the internal olefin sulfonate of component (A) is present in the carbon chain of the internal olefin sulfonate, that is, the olefin chain or alkane chain, as is apparent from the above-mentioned production method, and a part thereof There may be a trace amount of a sulfonic acid group present at the end of the carbon chain.
- the content of the internal olefin sulfonate in which the position of the sulfonic acid group is present at the 2-position of the carbon chain is low and is present in the interior.
- a high content of internal olefin sulfonate is preferred.
- the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position is preferably 30.0% by mass or less in the component (A) from the viewpoint of storage stability. More preferably, it is 28.0 mass% or less, More preferably, it is 25.0 mass% or less.
- the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position in the component (A) is preferably 10.0% by mass or more in the component (A) from the viewpoint of improving productivity. More preferably, it is 15.0 mass% or more, More preferably, it is 20.0 mass% or more.
- the content of the internal olefin sulfonate in which the sulfonic acid group is present at the 2-position is a viewpoint of storage stability, a viewpoint having a minimum viscosity that exhibits fluidity at a high concentration,
- a viewpoint of productivity improvement in a component (A), Preferably it is 10.0 to 30.0 mass%, More preferably, it is 15.0 to 28.0 mass%, More preferably, it is 20.0 mass% or more and 25.0 mass% or less.
- the content of the olefin sulfonate in which the sulfonic acid group is located at the 1-position of the olefin chain or alkane chain is preferably 3 in the component (A) from the viewpoint of storage stability. 0.0 mass% or less, more preferably 2.5 mass% or less, still more preferably 2.0 mass% or less, and preferably 0.01% from the viewpoint of reducing production costs and improving productivity. It is at least mass%.
- the content of the internal olefin sulfonate, in which the position of the sulfonic acid group is present from the 3rd position of the olefin chain or alkane chain, in the component (A) from the viewpoint of storage stability Preferably it is 60.0 mass% or more, More preferably, it is 65.0 mass% or more, More preferably, it is 70.0 mass% or more.
- the internal olefin sulfonate is preferably a mixture of a hydroxy body and an olefin body from the viewpoint of improving productivity and reducing impurities.
- the mass ratio (hydroxy body / olefin body) of the content of the hydroxy body of the internal olefin sulfonate and the content of the olefin body of the internal olefin sulfonate in the component (A) or the surfactant composition is productivity. From the viewpoint of improvement and impurity reduction, it is preferably 50/50 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0, and even more preferably. 75/25 to 100/0, and more preferably 75/25 to 95/5.
- the mass ratio of the content of the hydroxy compound of the internal olefin sulfonate and the content of the olefin compound of the internal olefin sulfonate in the component (A) is determined from the component (A) or the resulting surfactant composition by HPLC. After separating the hydroxy body and the olefin body by the method, it can be measured by the method described in Examples.
- the content of the component (A) is not limited in the surfactant composition of the present invention, from the viewpoint of storage stability and from the viewpoint of increasing the design freedom of the formulation in the final product using the surfactant composition of the present invention. 45.0% by mass or more, preferably 61.0% by mass or more, more preferably 62.0% by mass or more, still more preferably 63.0% by mass or more, and still more preferably It is 64.0 mass% or more.
- content of a component (A) is 70.0 mass% or less in the surfactant composition of this invention from a fluid viewpoint, Preferably it is 69.0 mass% or less, More Preferably it is 68.0 mass% or less, More preferably, it is 67.0 mass% or less, More preferably, it is 66.0 mass% or less.
- a component (A) is 45.0 mass% or more and 70.0 mass% or less in the surfactant composition of this invention, Comprising: Storage stability, Surfactant composition of this invention From the viewpoint of improving the degree of freedom of design of the formulation in the final product using the product and exhibiting the fluidity in a well-balanced manner, it is preferably 61.0 to 70.0% by mass, more preferably 62.0 to 70.%. 0 mass%, more preferably 62.0 to 69.0 mass%, still more preferably 63.0 to 68.0 mass%, still more preferably 64.0 to 67.0 mass%. More preferably, it is 64.0 to 66.0% by mass.
- the content of the component (A) is mainly determined from the viewpoint of storage stability and the surfactant composition of the present invention from the viewpoint of increasing the degree of freedom in designing the formulation in the final product using the surfactant composition of the present invention. More preferably, it is 64.0 mass% or more, More preferably, it is 66.0 mass% or more, More preferably, it is 67.0 mass% or more, More preferably, it is 68.0 mass%. % Or more and 70.0 mass% or less.
- the content of the component (A) is mainly determined from the viewpoint of storage stability and the surfactant composition of the present invention from the viewpoint of increasing the degree of freedom in designing the formulation in the final product using the surfactant composition of the present invention. In the product, it is more preferably 64.0 to 70.0% by mass, still more preferably 66.0 to 70.0% by mass, still more preferably 67.0 to 70.0% by mass. More preferably, it is 68.0 to 70.0% by mass.
- the content of the component (A) is more preferably 62.0% by mass or more, and further preferably 68.0% by mass or less in the surfactant composition of the present invention mainly from the viewpoint of fluidity. More preferably, it is 67.0 mass% or less, More preferably, it is 66.0 mass% or less, More preferably, it is 65.0 mass% or less.
- the content of component (A) is more preferably 62.0 to 68.0% by mass in the surfactant composition of the present invention mainly from the viewpoint of fluidity, and still more preferably 62.
- the amount is 0 to 67.0% by mass, more preferably 62.0 to 66.0% by mass, and still more preferably 62.0 to 65.0% by mass.
- the component (A) can be produced by sulfonating, neutralizing and hydrolyzing an internal olefin having 16 to 18 carbon atoms as a raw material.
- the sulfonation reaction can be performed by reacting 1.0 to 1.2 mol of sulfur trioxide gas with respect to 1 mol of the internal olefin.
- the reaction temperature can be 20 to 40 ° C.
- Neutralization is carried out by reacting an alkali aqueous solution such as sodium hydroxide, ammonia, 2-aminoethanol, etc. in an amount of 1.0 to 1.5 mole times the theoretical value of the sulfonic acid group.
- the hydrolysis reaction may be performed at 90 to 200 ° C. for 30 minutes to 3 hours in the presence of water. These reactions can be performed continuously. Moreover, after completion
- the raw material internal olefin having a distribution of 16 to 18 carbon atoms may be used for sulfonation, neutralization and hydrolysis treatment, and a single carbon
- the raw material internal olefin having a number may be subjected to sulfonation, neutralization, and hydrolysis treatments, and if necessary, a plurality of types of internal olefin sulfonates having different carbon numbers may be mixed in advance. Also good.
- the internal olefin refers to an olefin having a double bond inside the olefin chain as described above.
- the carbon number of the internal olefin is 16 or more and 18 or less.
- the internal olefin used may be used individually by 1 type, and may be used in combination of 2 or more type.
- the total content of the internal olefin in which the double bond in the raw material internal olefin exists at the 2-position Is preferably 45.0% by mass or less, more preferably 40.0% by mass or less, and further preferably 35.0% by mass or less in the raw material internal olefin from the viewpoint of storage stability and fluidity. It is.
- the total content of internal olefins in which the double bond in the raw material internal olefin is located at the 2-position is preferably 10.0% by mass in the raw material internal olefin from the viewpoint of reducing production costs and improving productivity. It is above, More preferably, it is 15.0 mass% or more, More preferably, it is 20.0 mass% or more, More preferably, it is 25.0 mass% or more.
- the total content of the internal olefin having a double bond in the 2-position in the raw material internal olefin is preferably 10.0 mass in the raw material internal olefin from the viewpoints of storage stability, fluidity, and productivity. % To 45.0% by mass, more preferably 15.0% to 40.0% by mass, still more preferably 20.0% to 35.0% by mass, and still more preferably. Is 25.0 mass% or more and less than 35.0 mass%.
- the content of an olefin having a double bond in the first position in the raw material internal olefin is preferably 3.0% by mass or less in the raw material internal olefin from the viewpoint of storage stability and fluidity. More preferably, it is 2.8 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less, Still more preferably, it is 1.0 mass% or less, and it is preferably 0.01 mass% or more from the viewpoint of reducing production cost and improving productivity.
- the total content of internal olefins in which the double bond in the raw material internal olefin exists from the 3rd position is preferably 50.0% by mass or more in the raw material internal olefin. More preferably, it is 60.0 mass% or more, More preferably, it is 65.0 mass% or more.
- the distribution of double bonds in the raw material internal olefin can be measured by, for example, a gas chromatograph mass spectrometer (hereinafter abbreviated as GC-MS). Specifically, each component having a different carbon chain length and double bond position is accurately separated by a gas chromatograph analyzer (hereinafter abbreviated as GC), and each is subjected to a mass spectrometer (hereinafter abbreviated as MS). Thus, the position of the double bond can be identified, and each ratio can be obtained from the GC peak area.
- GC-MS gas chromatograph mass spectrometer
- the surfactant composition of the present invention contains 0.5% by mass or more of an alpha olefin sulfonate having 12 to 14 carbon atoms (hereinafter also referred to as component (B)) from the viewpoint of storage stability and fluidity. 25.0 mass% or less is contained.
- the number of carbon atoms of the component (B) alpha-olefin sulfonate is preferably 12 or 14 from the viewpoint of availability, and 14 is preferable from the viewpoint of storage stability and fluidity.
- Examples of the salt of alpha olefin sulfonate include alkali metal salts, alkaline earth metal (1/2 atom) salts, ammonium salts, and organic ammonium salts.
- Examples of the alkali metal salt include Na salt and K salt.
- Component (B) can be produced by sulfonating, neutralizing and hydrolyzing the raw material alpha olefin having 12 to 14 carbon atoms (olefin having a double bond at the terminal on the carbon chain).
- the alpha olefin which is a raw material of the component (B) may be a simple substance having 12 or 14 carbon atoms, a mixture thereof, or a mixture of alpha olefins having other carbon numbers.
- Specific commercial products of such alpha olefins include “LIPOLAN LB-440”, “LIPOLAN PJ-400”, “LIPOLAN PB-800” manufactured by Lion Corporation, “ALFANOX46” manufactured by Kao Corporation, and Clariant.
- “Hostarpur OSB” manufactured by the company may be used.
- the content of the component (B) is 0.5% by mass or more, preferably 1.0% by mass or more, more preferably, in the surfactant composition of the present invention from the viewpoint of storage stability. Is 2.0% by mass or more, more preferably 3.0% by mass or more, and still more preferably 4.0% by mass or more.
- the content of the component (B) is included in the surfactant composition of the present invention from the viewpoint of fluidity and the degree of freedom in designing the formulation in the final product using the surfactant composition of the present invention. It is 25.0 mass% or less, Preferably it is 9.0 mass% or less, More preferably, it is 8.0 mass% or less, More preferably, it is 7.0 mass% or less, More preferably, it is It is 6.0 mass% or less.
- the content of the component (B) is 0.5% by mass or more and 25.0% by mass or less, preferably 1.0 to 9.0% by mass in the surfactant composition of the present invention. More preferably 1.0 to 8.0% by mass, still more preferably 2.0 to 7.0% by mass, still more preferably 3.0 to 6.0% by mass, and even more preferably.
- the content is preferably 4.0 to 6.0% by mass.
- the total content of component (A) and component (B) ((A) + (B)) is added to the surfactant composition of the present invention from the viewpoint of storage stability of the surfactant composition of the present invention. 66.0% by mass or more, preferably 68.0% by mass or more, more preferably 68.5% by mass or more, and further preferably 69.0% by mass or more.
- the total content of component (A) and component (B) ((A) + (B)) is 71.0% by mass or less in the surfactant composition of the present invention from the viewpoint of fluidity. And preferably it is 70.0 mass% or less.
- the total content of the component (A) and the component (B) ((A) + (B)) is selected from the viewpoint of exhibiting the storage stability and fluidity of the surfactant composition of the present invention in a balanced manner.
- the surfactant composition of the present invention it is 66.0% by mass or more and 71.0% by mass or less, preferably 68.0-70.0% by mass, more preferably 68.5-70.0% by mass. % By weight, more preferably 69.0 to 70.0% by weight.
- the total content ((A) + (B)) of the component (A) and the component (B) is 66.0% by mass or more in the surfactant composition of the present invention mainly from the viewpoint of fluidity.
- it is 69.5 mass% or less, More preferably, it is 69.0 mass% or less, More preferably, it is 68.5 mass% or less.
- the total content of component (A) and component (B) ((A) + (B)) is preferably 66.0 to preferably in the surfactant composition of the present invention mainly from the viewpoint of fluidity. It is 69.5% by mass, more preferably 66.0 to 69.0% by mass, and further preferably 66.0 to 68.5% by mass.
- the mass ratio ((A) / (B)) between the content of component (A) and the content of component (B) indicates the degree of freedom in designing the formulation in the final product using the surfactant composition of the present invention. From the viewpoint of enhancing, it is preferably 1.8 or more, more preferably 2.5 or more, still more preferably 5.0 or more, still more preferably 10.0 or more, and still more preferably 12. 5 or more. Further, the mass ratio ((A) / (B)) between the content of the component (A) and the content of the component (B) is preferably 140 or less, more preferably 75.
- the content of the component (A) and the content of the component (B) is preferably 1.8 to 140, more preferably 2.5 to 75.0, still more preferably 5.0 to 40.0. More preferably, it is 5.0 to 25.0, still more preferably 10.0 to 18.0, and still more preferably 12.5 to 15.0.
- the mass ratio ((A) / (B)) of the content of component (A) and the content of component (B) is mainly the design of the formulation in the final product using the surfactant composition of the present invention. From the viewpoint of increasing the degree of freedom, it is preferably 10.0 or more, more preferably 20.0 or more, still more preferably 40.0 or more, and preferably 75.0 or less. And the mass ratio ((A) / (B)) of the content of the component (A) and the content of the component (B) is mainly the design of the formulation in the final product using the surfactant composition of the present invention. From the viewpoint of increasing the degree of freedom, it is preferably 10.0 to 75.0, more preferably 20.0 to 75.0, and still more preferably 40.0 to 75.0.
- the surfactant composition of the present invention contains water (hereinafter also referred to as component (C)).
- water is not particularly limited, but purified water such as ion exchange water, distilled water, reverse osmosis membrane water, and pure water is preferable.
- the content of the component (C) is preferably 34.0% by mass or less, more preferably in the surfactant composition of the present invention, from the viewpoint of storage stability of the surfactant composition of the present invention. It is 32.0 mass% or less, More preferably, it is 31.0 mass% or less, More preferably, it is 30.5 mass% or less. Further, the content of the component (C) is preferably 24.0% by mass or more, more preferably 25.0% by mass or more in the surfactant composition of the present invention from the viewpoint of fluidity. More preferably, it is 26.0 mass% or more.
- the content of component (C) is preferably 24.0 to 34.0% by mass in the surfactant composition of the present invention from the viewpoint of storage stability and fluidity, and more preferably 25 It is 0.0 to 32.0% by mass, more preferably 25.0 to 31.0% by mass, and still more preferably 26.0 to 30.5% by mass.
- component (A) is obtained by sulfonating, neutralizing and hydrolyzing the internal olefin as described above, unreacted raw internal olefin and inorganic compound are contained in the surfactant composition of the present invention. May remain. It is preferable that the content of these components is small.
- the content of the unreacted raw material internal olefin in the surfactant composition of the present invention is determined from the viewpoint of foam performance and detergency in the final product using the surfactant composition of the present invention. In the agent composition, it is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and still more preferably 1.5% by mass. It is as follows. In addition, content of unreacted raw material internal olefin can be measured by the method as described in an Example.
- the content of the inorganic compound in the surfactant composition of the present invention is the same as that in the surfactant composition of the present invention from the viewpoint of foam performance and detergency in the final product using the surfactant composition of the present invention. Preferably, it is 5.0 mass% or less, More preferably, it is 3.0 mass% or less, More preferably, it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less.
- the inorganic compound includes a sulfate and an alkali agent, and the content of these inorganic compounds can be measured by potentiometric titration. Specifically, it can be measured by the method described in the examples.
- the surfactant composition of the present invention contains a surfactant other than the above component (A) and component (B) (hereinafter also referred to as component (D)) as long as the effects of the present invention are not impaired. Can do.
- the surfactant of the component (D) is a surfactant usually used in pharmaceuticals, quasi drugs, cosmetics, toiletries, miscellaneous goods, etc., and interfaces other than the components (A) and (B). Any surfactant can be used, and specific examples include anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants.
- an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant is preferable from the viewpoints of detergency, foaming properties, and foam quality improvement.
- the surfactant composition of the present invention appropriately contains other components that are usually used as raw materials for final products such as detergents, in addition to thinning agents, polyhydric alcohols, preservatives, and reducing agents. can do.
- Such components include feel improvers, thickeners, fragrances, UV absorbers, visible light absorbers, chelating agents, antioxidants, colorants, preservatives, pH adjusters, viscosity adjusters, pearl brighteners, wetting Agents and the like.
- the surfactant composition of the present invention is a viewpoint that combines good fluidity and excellent storage stability, and from the viewpoint of increasing the design freedom of the formulation in the final product using the surfactant composition of the present invention,
- the viscosity at 25 ° C. is preferably 5 Pa ⁇ s or more, more preferably 10 Pa ⁇ s or more, still more preferably 30 Pa ⁇ s or more, still more preferably 60 Pa ⁇ s or more, and still more preferably.
- 68 Pa ⁇ s or more preferably 155 Pa ⁇ s or less, more preferably 130 Pa ⁇ s or less, still more preferably 110 Pa ⁇ s or less, still more preferably 95 Pa ⁇ s or less, and even more preferably.
- the surfactant composition of the present invention has a viscosity at 25 ° C. of preferably 5 to 155 Pa ⁇ s, more preferably 10 to 130 Pa ⁇ s, still more preferably 30 to 110 Pa ⁇ s, More preferably, it is 60 to 95 Pa ⁇ s, and still more preferably 68 to 80 Pa ⁇ s.
- the viscosity at 25 ° C. of the surfactant composition of the present invention means a value measured by the method described in Examples.
- ⁇ Method for producing surfactant composition> There is no restriction
- the surfactant composition of the present invention can be suitably used as a base for various cleaning agents excellent in stability and fluidity.
- Specific examples of such cleaners include clothing cleaners, dish cleaners, hair cleaners, body cleaners, precision parts cleaners, and hard surface cleaners.
- These detergents can be produced by mixing the surfactant composition of the present invention and other components together with water as necessary.
- the other components mean components other than the above components (A) and (B), components usually used as raw materials for the above-mentioned various cleaning agents as final products, and the like.
- the present invention further discloses the following surfactant composition.
- the total content of component (A) and component (B) ((A) + (B)) is preferably 68.0% by mass or more, more preferably 68.5% by mass or more, More preferably, it is 69.0 mass% or more, Preferably it is 70.0 mass% or less, The surfactant composition of said [1].
- the total content of component (A) and component (B) ((A) + (B)) is 66.0% by mass or more, preferably 69.5% by mass or less, more preferably Is 69.0 mass% or less, More preferably, it is 68.5 mass% or less, The surfactant composition of said [1].
- the mass ratio ((A) / (B)) between the content of component (A) and the content of component (B) is preferably 1.8 or more, more preferably 2.5 or more. More preferably 5.0 or more, still more preferably 10.0 or more, still more preferably 12.5 or more, preferably 140 or less, more preferably 75.0 or less. More preferably, it is 40.0 or less, more preferably 25.0 or less, even more preferably 18.0 or less, and still more preferably 15.0 or less. ] Any 1 surfactant composition. [5] The mass ratio ((A) / (B)) between the content of component (A) and the content of component (B) is preferably 10.0 or more, more preferably 20.0 or more. The surfactant composition according to any one of [1] to [3], which is more preferably 40.0 or more and preferably 75.0 or less.
- the content of component (A) is preferably 61.0% by mass or more, more preferably 62.0% by mass or more, still more preferably 63.0% by mass or more, and still more preferably Is 64.0% by mass or more, preferably 69.0% by mass or less, more preferably 68.0% by mass or less, still more preferably 67.0% by mass or less, and still more preferably 66%.
- the surfactant composition according to any one of the above [1] to [5], which is 0.0 mass% or less.
- the content of the component (A) is more preferably 64.0% by mass or more, still more preferably 66.0% by mass or more, still more preferably 67.0% by mass or more, The surfactant composition according to any one of the above [1] to [5], which is more preferably 68.0% by mass or more and 70% by mass or less.
- the content of the component (A) is more preferably 62.0% by mass or more, further preferably 68.0% by mass or less, still more preferably 67.0% by mass or less, and more The surfactant composition according to any one of [1] to [5] above, further preferably 66.0% by mass or less, and still more preferably 65.0% by mass or less.
- Mass ratio of content of internal olefin sulfonate having 16 carbon atoms and content of internal olefin sulfonate having 18 carbon atoms in component (A) (internal olefin sulfonate having 16 carbon atoms / carbon number) 18 internal olefin sulfonate) is preferably 100/0 to 40/60, more preferably 95/5 to 50/50, and still more preferably 90/10 to 70/30.
- Any one surfactant composition is preferably 100/0 to 40/60, more preferably 95/5 to 50/50, and still more preferably 90/10 to 70/30.
- the content of the olefin sulfonate in which the position of the sulfonic acid group is at the 1st position of the olefin chain or alkane chain is preferably 3.0% by mass or less, more preferably
- the content of the internal olefin sulfonate having a sulfonic acid group at the 2-position in the component (A) is preferably 30.0% by mass or less, more preferably 28.0% by mass or less.
- the surfactant composition according to any one of [11].
- the content of the olefin sulfonate in which the position of the sulfonic acid group in the component (A) is present from the 3rd position of the olefin chain or alkane chain is preferably 60.0% by mass or more, and more
- the mass ratio (hydroxy body / olefin body) of the content of the hydroxy body of the internal olefin sulfonate and the content of the olefin body of the internal olefin sulfonate in the component (A) or the surfactant composition is , Preferably 50/50 to 100/0, more preferably 60/40 to 100/0, still more preferably 70/30 to 100/0, and even more preferably 75/25 to 100/0.
- the surfactant composition according to any one of [1] to [13] above, which is more preferably 75/25 to 95/5.
- the content of component (B) is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, still more preferably 4.0% by mass or more, and preferably 9%.
- the content of component (C) is preferably 34.0% by mass or less, more preferably 32.0% by mass or less, still more preferably 31.0% by mass or less, and still more preferably Is 30.5% by mass or less, preferably 24.0% by mass or more, more preferably 25.0% by mass or more, and still more preferably 26.0% by mass or more.
- Any one surfactant composition is preferably 34.0% by mass or less, more preferably 32.0% by mass or less, still more preferably 31.0% by mass or less, and still more preferably Is 30.5% by mass or less, preferably 24.0% by mass or more, more preferably 25.0% by mass or more, and still more preferably 26.0% by mass or more.
- Any one surfactant composition is preferably 34.0% by mass or less, more preferably 32.0% by mass or less, still more preferably 31.0% by mass or less, and still more preferably Is 30.5% by mass or less, preferably 24.0% by mass or more, more preferably 25.0%
- the viscosity of the surfactant composition of the present invention at 25 ° C is preferably 5 Pa ⁇ s or more, more preferably 10 Pa ⁇ s or more, still more preferably 30 Pa ⁇ s or more, and even more preferably.
- a detergent base is a clothes detergent base, a dish detergent base, a hair detergent base, a body detergent base, and a precision parts detergent base. Or use of said [22] which is a base for detergents for hard surfaces.
- a detergent base is a clothes detergent base, a dish detergent base, a hair detergent base, a body detergent base, and a precision parts detergent base. Or use of said [22] which is a base for detergents for hard surfaces.
- the cleaning agent is a clothing detergent, a dish cleaner, a hair cleaner, a body cleaner, a precision part cleaner, or a hard surface cleaner.
- [26] Usually used as a raw material for the surfactant composition according to any one of [1] to [21], a surfactant other than the component (A) and the component (B), and a cleaning agent as a final product.
- the manufacturing method of the cleaning composition which has the process of mixing the 1 type (s) or 2 or more types chosen from a component, and water.
- Measurement conditions (i) Method for measuring double bond position of raw material internal olefin The double bond position of internal olefin was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, dimethyl disulfide was reacted with an internal olefin to obtain a dithiolated derivative, and then each component was separated by GC. As a result, the double bond position of the internal olefin was determined from each peak area.
- the apparatus and analysis conditions used for the measurement are as follows.
- GC device “HP6890” manufactured by HEWLETT PACKARD
- column “Ultra-Alloy-1HT capillary column” (30 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m, manufactured by Frontier Laboratories), detector (hydrogen flame ion detector (FID))
- Injection temperature 300 ° C detector temperature 350 ° C
- HPLC device “Agilent Technology 1100” manufactured by Agilent Technologies
- column “L-columnODS” 4.6 ⁇ 150 mm, manufactured by Chemicals Research Institute
- sample preparation diluted 1000 times with methanol
- eluent A 10 mM ammonium acetate added water
- eluent B 10 mM ammonium acetate added methanol
- MS device “Agilent Technology 1100MS SL (G1946D)” manufactured by Agilent Technologies
- MS Detection negative ion detection m / z 60-1600, UV 240 nm
- GC device “Agilent Technology 6850” (manufactured by Agilent Technologies), column “Ultra-Alloy-1HT capillary column” (15 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m, manufactured by Frontier Laboratories), detector (hydrogen ion detector (FID) )), Injection temperature 300 ° C., detector temperature 350 ° C., He flow rate 3.8 mL / min
- (Iv) Measuring method of content of inorganic compound The content of the inorganic compound was measured by potentiometric titration or neutralization titration. Specifically, the content of Na 2 SO 4 was quantified by determining the sulfate radical (SO 4 2 ⁇ ) by potentiometric titration using an SO 4 electrode. The content of NaOH was quantified by neutralization titration with dilute hydrochloric acid.
- the obtained crude internal olefin was transferred to a distillation flask and distilled at 136 to 160 ° C./4.0 mmHg to obtain a C16 internal olefin having an olefin purity of 100%.
- the double bond distribution of the obtained internal olefin was C1 position 1.6 mass%, C2 position 29.7 mass%, C3 position 24.9 mass%, C4 position 18.7 mass%, C5 position 12.2 mass%. %, C6 position 6.7% by mass, C7, position 8 total was 6.2% by mass.
- the obtained crude internal olefin was transferred to a distillation flask and distilled at 148 to 158 ° C./0.5 mmHg to obtain an 18-carbon internal olefin having an olefin purity of 100%.
- the resulting double bond distribution of the internal olefin was 1.6 mass% at C1 position, 30.6 mass% at C2 position, 24.8 mass% at C3 position, 18.6 mass% at C4 position, 11.1 mass at C5 position. %, C6 position 6.5 mass%, C7 position 3.7 mass%, C8, 9th position total was 3.0 mass%.
- the obtained sulfonated product was added to an alkaline aqueous solution to which sodium hydroxide was added so as to be 1.2 mol times the theoretical acid value (AV), and neutralized at 30 ° C. for 1 hour with stirring.
- a salt composition (IOS-1) was obtained.
- component (A) In IOS-1, the content of component (A) was 96.7% by mass, the content of raw material internal olefins was 1.8% by mass, and the content of inorganic compounds was 1.5% by mass.
- the mass ratio of the hydroxy body / olefin body in the component (A) is 85/15, the content of the alpha olefin sulfonate in the component (A) is 1.9% by mass, and the position of the hydrophilic group in the component (A) is The content of the 2-position internal olefin sulfonate was 23.0% by mass.
- a 16-carbon internal olefin sulfonic acid sodium salt composition (IOS-2) was obtained under the same conditions as in Production Example 1 except that the 16-carbon internal olefin produced in Production Example A was used.
- the content of component (A) was 97.2% by mass
- the content of raw material internal olefins was 1.5% by mass
- the content of inorganic compounds was 1.3% by mass.
- the mass ratio of the hydroxy body / olefin body in the component (A) is 85/15, the content of the alpha olefin sulfonate in the component (A) is 2.0 mass%, and the hydrophilic group position in the component (A) is The content of the 2-position internal olefin sulfonate was 22.0% by mass.
- AOS-2 is obtained by freeze-drying sodium alpha olefin sulfonate "Alpha Knox 46" having 14 and 16 carbon atoms (manufactured by Kao Corporation, content of carbon 14 having 60% by mass, active ingredient 38%). It was. In AOS-2, the water content was 0 mass%, and the content of sodium alpha olefin sulfonate having 14 and 16 carbon atoms was 94.8 mass%.
- Examples 1 to 13, Comparative Examples 1 to 9 According to the composition shown in Table 1, the internal olefin sulfonate (component (A)), the alpha olefin sulfonate (component (B)) obtained by Production Examples 1 and 2 and purified water were used. The mixture was uniformly mixed at 0 ° C., placed in a sealed container, and allowed to stand overnight in a thermostatic bath (80 ° C.). Next, the mixture was stirred at 50 ° C. or higher, and 20 g of each obtained surfactant composition was accommodated in three 50 mL centrifuge tubes. Each centrifuge tube was stored at 40 ° C., 25 ° C., and 15 ° C. for 1 day, fluidity was evaluated according to the following method, viscosity was measured, and storage stability was also evaluated. The results are shown in Table 1, including the evaluation results of the measured surfactant compositions.
- a centrifuge “Hitachi high-speed cooling centrifuge CR21GIII” (manufactured by Hitachi Koki Co., Ltd., rotor No .: R15A) is used. What was centrifuged at 5000 r / min was used. At the time of 12 minutes (corresponding to 1 month), 36 minutes (corresponding to 3 months), and 72 minutes (corresponding to 6 months) corresponding to the equivalent centrifugation time for which the storage period is 1 month, 3 months and 6 months
- the stored products were evaluated visually according to the following criteria.
- a preserved product at 15 ° C. a product treated in the same manner as the preserved product at 25 ° C.
- a hair shampoo having the following composition was prepared according to a conventional method. Specifically, after taking purified water in a beaker, adding cationized guar gum and dispersing uniformly, the mixture was heated to 80 ° C., and the surfactant composition obtained in Example 7, coconut oil fatty acid amidopropyl Betaine, coconut oil fatty acid monoethanolamide, and sodium benzoate were added and mixed uniformly. Then, it cooled to 40 degreeC, the ethylene glycol distearate was disperse
- This hair shampoo was excellent in foaming properties and cleanability and had an excellent feeling of use.
- the surfactant composition of the present invention is a base for cleaning agents in a wide range of fields such as clothing cleaners, dish cleaners, hair cleaners, body cleaners, precision parts cleaners, and hard surface cleaners. As an agent, it can utilize suitably.
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Abstract
Description
(A)炭素数16以上18以下の内部オレフィンスルホン酸塩 45.0質量%以上70.0質量%以下、
(B)炭素数12以上14以下のアルファオレフィンスルホン酸塩 0.5質量%以上25.0質量%以下、及び
(C)水
を含有し、かつ成分(A)及び成分(B)の合計含有量が、66.0質量%以上71.0質量%以下である界面活性剤組成物に関する。
本発明の界面活性剤組成物は、次の成分(A)、(B)、及び(C):
(A)炭素数16以上18以下の内部オレフィンスルホン酸塩 45.0質量%以上70.0質量%以下、
(B)炭素数12以上14以下のアルファオレフィンスルホン酸塩 0.5質量%以上25.0質量%以下、及び
(C)水
を含有し、かつ成分(A)及び成分(B)の合計含有量が、66.0質量%以上71.0質量%以下である。
一般に、成分(A)の炭素数16以上18以下の内部オレフィンスルホン酸塩を高濃度で含有する組成物では、系中でミセル相とラメラ相の2相が存在し、それらの比重差によって相分離が生じると考えられるところ、本発明では、成分(B)として特定量の炭素数の短い炭素数12以上14以下のアルファオレフィンスルホン酸塩を含有することにより、こうしたミセル相の減少や消失により相分離が効果的に抑制されると考えられる。一方、成分(A)の炭素数16以上18以下の内部オレフィンスルホン酸塩に含まれる炭素数16以上18以下のアルファオレフィンスルホン酸塩が析出物となり得るところ、炭素数の短い成分(B)の炭素数12以上14以下のアルファオレフィンスルホン酸塩によって溶解性が向上し、析出物の生成が効果的に抑制されると考えられる。さらに、ミセル相が減少又は消失して、かかる成分(B)を含む混合ラメラ相が形成されるため、流動性も向上すると考えられる。
本発明の界面活性剤組成物は、かかる組成物を用いた洗浄剤等の最終製品における起泡性や洗浄性に優れる観点から、炭素数16以上18以下の内部オレフィンスルホン酸塩(以下、成分(A)ともいう。)を45.0質量%以上70.0質量%以下含有する。
なお、上記質量比は、高速液体クロマトグラフィー質量分析計(以下、HPLC-MSと省略)により測定できる。具体的には、成分(A)又は得られる界面活性剤組成物から、HPLCにより炭素数16の内部オレフィンスルホン酸塩と炭素数18の内部オレフィンスルホン酸塩を分離し、それぞれをMSにかけることで同定でき、そのHPLC-MSピーク面積から質量比を求めることができる。
スルホン化反応は、内部オレフィン1モルに対し三酸化硫黄ガスを1.0~1.2モル反応させることにより行うことができる。反応温度は、20~40℃で行うことができる。
中和は、スルホン酸基の理論値に対し1.0~1.5モル倍量の水酸化ナトリウム、アンモニア、2-アミノエタノール等のアルカリ水溶液を反応させることにより行なわれる。加水分解反応は、水の存在下90~200℃で30分~3時間反応を行えばよい。これらの反応は、連続して行うことができる。また反応終了後は、抽出、洗浄等により精製することができる。
本発明の界面活性剤組成物は、保存安定性と流動性の観点から、炭素数12以上14以下のアルファオレフィンスルホン酸塩(以下、成分(B)ともいう。)を0.5質量%以上25.0質量%以下含有する。成分(B)のアルファオレフィンスルホン酸塩の炭素数は、入手性の観点から、12、14が好ましく、保存安定性と流動性の観点から、14が好ましい。
成分(A)は、前述のように内部オレフィンをスルホン化、中和、加水分解することにより得られることから、本発明の界面活性剤組成物中には、未反応の原料内部オレフィン及び無機化合物が残存する可能性がある。これらの成分の含有量は少ないほうが好ましい。
本発明の界面活性剤組成物中における未反応の原料内部オレフィンの含有量は、本発明の界面活性剤組成物を用いた最終製品における泡性能及び洗浄性等の観点から、本発明の界面活性剤組成物中に、好ましくは5.0質量%以下であり、より好ましくは3.0質量%以下であり、更に好ましくは2.0質量%以下であり、より更に好ましくは1.5質量%以下である。
なお、未反応の原料内部オレフィンの含有量は、実施例に記載の方法により測定することができる。
ここで、無機化合物には、硫酸塩、アルカリ剤が含まれ、これらの無機化合物の含有量は、電位差滴定により測定することができる。具体的には、実施例に記載の方法により測定することができる。
なお、本発明の界面活性剤組成物の25℃における粘度とは、実施例に記載の方法により測定される値を意味する。
本発明の界面活性剤組成物の製造方法には特に制限はなく、常法により製造することができる。具体的には、例えば、成分(A)、成分(B)、必要に応じて成分(D)或いはその他の成分、及び水(成分(C))を加温し、均一混合する。成分(A)は、必要に応じて、予め水に分散又は溶解させた後に添加してもよい。
本発明の界面活性剤組成物は、安定性と流動性に優れた各種洗浄剤用基剤として、好適に用いることができる。かかる洗浄剤としては、具体例には、衣料用洗浄剤、食器用洗浄剤、毛髪用洗浄剤、身体用洗浄剤、精密部品用洗浄剤、硬質表面用洗浄剤等が挙げられる。これらの洗浄剤は、本発明の界面活性剤組成物と、必要に応じてその他の成分を水とともに混合することにより製造することができる。
なお、その他の成分とは、上記成分(A)及び成分(B)以外の界面活性剤や、最終製品である上記各種洗浄剤の原料として通常用いられる成分等を意味する。
[1]次の成分(A)、(B)、及び(C):
(A)炭素数16以上18以下の内部オレフィンスルホン酸塩 45.0質量%以上70.0質量%以下、
(B)炭素数12以上14以下のアルファオレフィンスルホン酸塩 0.5質量%以上25.0質量%以下、及び
(C)水
を含有し、かつ成分(A)及び成分(B)の合計含有量が、66.0質量%以上71.0質量%以下である界面活性剤組成物。
[2]成分(A)と成分(B)の合計含有量((A)+(B))が、好ましくは68.0質量%以上であり、より好ましくは68.5質量%以上であり、更に好ましくは69.0質量%以上であり、好ましくは70.0質量%以下である上記[1]の界面活性剤組成物。
[3]成分(A)と成分(B)の合計含有量((A)+(B))が、66.0質量%以上であって、好ましくは69.5質量%以下であり、より好ましくは69.0質量%以下であり、更に好ましくは68.5質量%以下である上記[1]の界面活性剤組成物。
[4]成分(A)の含有量と成分(B)の含有量との質量比((A)/(B))が、好ましくは1.8以上であり、より好ましくは2.5以上であり、更に好ましくは5.0以上であり、より更に好ましくは10.0以上であり、より更に好ましくは12.5以上であり、好ましくは140以下であり、より好ましくは75.0以下であり、更に好ましくは40.0以下であり、より更に好ましくは25.0以下であり、より更に好ましくは18.0以下であり、より更に好ましくは15.0以下である上記[1]~[3]いずれか1の界面活性剤組成物。
[5]成分(A)の含有量と成分(B)の含有量との質量比((A)/(B))が、好ましくは10.0以上であり、より好ましくは20.0以上であり、更に好ましくは40.0以上であり、好ましくは75.0以下である上記[1]~[3]いずれか1の界面活性剤組成物。
[7]成分(A)の含有量が、更に好ましくは64.0質量%以上であり、より更に好ましくは66.0質量%以上であり、より更に好ましくは67.0質量%以上であり、より更に好ましくは68.0質量%以上であり、70質量%以下である上記[1]~[5]いずれか1の界面活性剤組成物。
[8]成分(A)の含有量が、更に好ましくは62.0質量%以上であり、更に好ましくは68.0質量%以下であり、より更に好ましくは67.0質量%以下であり、より更に好ましくは66.0質量%以下であり、より更に好ましくは65.0質量%以下である上記[1]~[5]いずれか1の界面活性剤組成物。
[10]成分(A)における炭素数16の内部オレフィンスルホン酸塩の含有量と炭素数18の内部オレフィンスルホン酸塩の含有量との質量比(炭素数16の内部オレフィンスルホン酸塩/炭素数18の内部オレフィンスルホン酸塩)が、好ましくは100/0~40/60であり、より好ましくは95/5~50/50であり、更に好ましくは90/10~70/30である上記[1]~[9]いずれか1の界面活性剤組成物。
[11]成分(A)中における、スルホン酸基の位置がオレフィン鎖又はアルカン鎖の1位に存在するオレフィンスルホン酸塩の含有量が、好ましくは3.0質量%以下であり、より好ましくは2.5質量%以下であり、更に好ましくは2.0質量%以下であり、好ましくは0.01質量%以上である上記[1]~[10]いずれか1の界面活性剤組成物。
[12]成分(A)中における、スルホン酸基が2位に存在する内部オレフィンスルホン酸塩の含有量が、好ましくは30.0質量%以下であり、より好ましくは28.0質量%以下であり、更に好ましくは25.0質量%以下であり、好ましくは10.0質量%以上であり、より好ましくは15.0質量%以上であり、更に好ましくは20.0質量%以上である上記[1]~[11]いずれか1の界面活性剤組成物。
[13]成分(A)中における、スルホン酸基の位置がオレフィン鎖又はアルカン鎖の3位から内側に存在するオレフィンスルホン酸塩の含有量が、好ましくは60.0質量%以上であり、より好ましくは65.0質量%以上であり、更に好ましくは70.0質量%以上である上記[1]~[12]いずれか1の界面活性剤組成物。
[14]成分(A)又は界面活性剤組成物中における内部オレフィンスルホン酸塩のヒドロキシ体の含有量と内部オレフィンスルホン酸塩のオレフィン体の含有量との質量比(ヒドロキシ体/オレフィン体)が、好ましくは50/50~100/0であり、より好ましくは60/40~100/0であり、更に好ましくは70/30~100/0であり、また更に好ましくは75/25~100/0であり、またより好ましくは75/25~95/5である上記[1]~[13]いずれか1の界面活性剤組成物。
[16]成分(B)のアルファオレフィンスルホン酸塩の炭素数が、好ましくは12、14であり、また好ましくは14である上記[1]~[15]いずれか1の界面活性剤組成物。
[17]成分(C)の含有量が、好ましくは34.0質量%以下であり、より好ましくは32.0質量%以下であり、更に好ましくは31.0質量%以下であり、より更に好ましくは30.5質量%以下であり、好ましくは24.0質量%以上であり、より好ましくは25.0質量%以上であり、より更に好ましくは26.0質量%以上である上記[1]~[16]いずれか1の界面活性剤組成物。
[18]成分(A)及び成分(B)の合計含有量が、69.0質量%以上71.0質量%以下である上記[1]~[17]いずれか1の界面活性剤組成物。
[19]成分(A)の含有量が、61.0質量%以上69.0質量%以下である上記[1]~[18]いずれか1の界面活性剤組成物。
[20]成分(B)の含有量が、1.0質量%以上6.0質量%以下である上記[1]~[19]いずれか1の界面活性剤組成物。
[21]本発明の界面活性剤組成物の25℃における粘度が、好ましくは5Pa・s以上であり、より好ましくは10Pa・s以上であり、更に好ましくは30Pa・s以上であり、より更に好ましくは60Pa・s以上であり、より更に好ましくは68Pa・s以上であり、好ましくは155Pa・s以下であり、より好ましくは130Pa・s以下であり、更に好ましくは110Pa・s以下であり、より更に好ましくは95Pa・s以下であり、より更に好ましくは80Pa・s以下である上記[1]~[17]いずれか1の界面活性剤組成物。
[23]洗浄剤用基剤が、衣料用洗浄剤用基剤、食器用洗浄剤用基剤、毛髪用洗浄剤用基剤、身体用洗浄剤用基剤、精密部品用洗浄剤用基剤、又は硬質表面用洗浄剤用基剤である上記[22]の使用。
[24]上記[1]~[21]いずれか1の界面活性剤組成物の、洗浄剤製造のための使用。
[25]洗浄剤が、衣料用洗浄剤洗剤、食器用洗浄剤、毛髪用洗浄剤、身体用洗浄剤、精密部品用洗浄剤、又は硬質表面用洗浄剤である上記[24]の使用。
[26]上記[1]~[21]いずれか1の界面活性剤組成物と、成分(A)及び成分(B)以外の界面活性剤、並びに最終製品である洗浄剤の原料として通常用いられる成分から選ばれる1種又は2種以上と、水とを混合する工程を有する洗浄剤組成物の製造方法。
また、各種物性の測定法は以下のとおりである。
(i)原料内部オレフィンの二重結合位置の測定方法
内部オレフィンの二重結合位置は、ガスクロマトグラフィー(以下、GCと省略)により測定した。具体的には、内部オレフィンに対しジメチルジスルフィドを反応させることでジチオ化誘導体とした後、各成分をGCで分離した。結果、それぞれのピーク面積より内部オレフィンの二重結合位置を求めた。
尚、測定に使用した装置及び分析条件は次の通りである。GC装置「HP6890」(HEWLETT PACKARD社製)、カラム「Ultra-Alloy-1HTキャピラリーカラム」(30m×250μm×0.15μm、フロンティア・ラボ株式会社製)、検出器(水素炎イオン検出器(FID))、インジェクション温度300℃、ディテクター温度350℃、He流量4.6mL/分
ヒドロキシ体/オレフィン体の質量比は、HPLC-MSにより測定した。具体的には、HPLCによりヒドロキシ体とオレフィン体を分離し、それぞれをMSにかけることで同定した。結果、そのHPLC-MSピーク面積から各々の割合を求めた。
尚、測定に使用した装置及び条件は次の通りである。HPLC装置「アジレントテクノロジー1100」(アジレントテクノロジー社製)、カラム「L-columnODS」(4.6×150mm、一般財団法人化学物質評価研究機構製)、サンプル調製(メタノールで1000倍希釈)、溶離液A(10mM酢酸アンモニウム添加水)、溶離液B(10mM酢酸アンモニウム添加メタノール)、グラジェント(0分(A/B=30/70%)→10分(30/70%)→55分(0/100%)→65分(0/100%)→66分(30/70%)→75分(30/70%)、MS装置「アジレントテクノロジー1100MS SL(G1946D)」(アジレントテクノロジー社製)、MS検出(陰イオン検出 m/z60-1600、UV240nm)
原料内部オレフィンの含有量は、GCにより測定した。具体的には、内部オレフィンスルホン酸塩水溶液にエタノールと石油エーテルを添加した後、抽出し石油エーテル相にオレフィンを得た。結果、そのGCピーク面積から原料内部オレフィン量を定量した。尚、測定に使用した装置及び分析条件は次の通りである。GC装置「アジレントテクノロジー6850」(アジレントテクノロジー社製)、カラム「Ultra-Alloy-1HTキャピラリーカラム」(15m×250μm×0.15μm、フロンティア・ラボ株式会社製)、検出器(水素炎イオン検出器(FID))、インジェクション温度300℃、ディテクター温度350℃、He流量3.8mL/分
無機化合物の含有量は、電位差滴定や中和滴定により測定した。具体的には、Na2SO4の含有量は、硫酸根(SO4 2-)をSO4電極を用いた電位差滴定によって求めることで定量した。また、NaOHの含有量は、希塩酸で中和滴定することで定量した。
[製造例A]
攪拌装置付きフラスコに1-ヘキサデカノール「カルコール6098」(花王株式会社製)15000g(61.9モル)、固体酸触媒としてγ―アルミナ(STREM Chemicals,Inc社)750g(原料アルコールに対して5質量%)を仕込み、攪拌下、280℃にて系内に窒素(7000mL/分)を流通させながら8時間、反応を行った。反応終了後のアルコール転化率は100%、C16内部オレフィン純度は99.7%であった。得られた粗内部オレフィンを蒸留用フラスコに移し、136~160℃/4.0mmHgで蒸留することでオレフィン純度100%の炭素数16の内部オレフィンを得た。得られた内部オレフィンの二重結合分布は、C1位1.6質量%、C2位29.7質量%、C3位24.9質量%、C4位18.7質量%、C5位12.2質量%、C6位6.7質量%、C7、8位の合計が6.2質量%であった。
攪拌装置付きフラスコに1-オクタデカノール「カルコール8098」(花王株式会社製)15000g(55.5モル)、固体酸触媒としてγ―アルミナ(STREM Chemicals,Inc社)750g(原料アルコールに対して5質量%)を仕込み、攪拌下、280℃にて系内に窒素(7000mL/分)を流通させながら12時間、反応を行った。反応終了後のアルコール転化率は100%、C18内部オレフィン純度は98.5%であった。得られた粗内部オレフィンを蒸留用フラスコに移し、148-158℃/0.5mmHgで蒸留することでオレフィン純度100%の炭素数18の内部オレフィンを得た。得られた内部オレフィンの二重結合分布は、C1位1.6質量%、C2位30.6質量%、C3位24.8質量%、C4位18.6質量%、C5位11.1質量%、C6位6.5質量%、C7位3.7質量%,C8、9位の合計が3.0質量%であった。
[製造例1]
製造例A、Bで製造した炭素数16、18の内部オレフィンを、それぞれ質量比8:2になるように混合し、得られた内部オレフィンを、薄膜式スルホン化反応器(内径14mmφ、長さ4m)を使用してSO3濃度2.8容量%の三酸化硫黄ガス、反応器外部ジャケットに10℃の冷却水を通液することでスルホン化反応を行った。尚、SO3/内部オレフィン反応モル比は1.02に設定した。
得られたスルホン化物を、理論酸価(AV)に対し1.2モル倍になるよう水酸化ナトリウムを添加したアルカリ水溶液へ添加し、攪拌しながら30℃、1時間中和した。中和物をオートクレーブ中で160℃、1時間加熱することで加水分解を行った後に、凍結乾燥により水分を除去し、炭素数C16/18=8/2(質量比)の内部オレフィンスルホン酸ナトリウム塩組成物(IOS-1)を得た。このIOS-1中、成分(A)の含有量は96.7質量%、原料内部オレフィンの含有量は1.8質量%、無機化合物の含有量は1.5質量%であった。成分(A)中のヒドロキシ体/オレフィン体の質量比は85/15、成分(A)中のアルファオレフィンスルホン酸塩の含有量は1.9質量%、成分(A)中の親水基位置が2位の内部オレフィンスルホン酸塩の含有量は23.0質量%であった。
製造例Aで製造した炭素数16の内部オレフィンを用いた以外は、製造例1と同様の条件で、炭素数16の内部オレフィンスルホン酸ナトリウム塩組成物(IOS-2)を得た。このIOS-2中、成分(A)の含有量は97.2質量%、原料内部オレフィンの含有量は1.5質量%、無機化合物の含有量は1.3質量%であった。成分(A)中のヒドロキシ体/オレフィン体の質量比は85/15、成分(A)中のアルファオレフィンスルホン酸塩の含有量は2.0質量%、成分(A)中の親水基位置が2位の内部オレフィンスルホン酸塩の含有量は22.0質量%であった。
[製造例3]
炭素数14のアルファオレフィンスルホン酸ナトリウム「リポランLB-440」(ライオン株式会社製、有効成分36%)を凍結乾燥により水分を除去し、AOS-1を得た。AOS-1中、水分含有量は0質量%、炭素数14のアルファオレフィンスルホン酸ナトリウムの含有量は92.5質量%であった。
炭素数14及び16のアルファオレフィンスルホン酸ナトリウム「アルファノックス46」(花王株式会社製、炭素数14の含量60質量%、有効成分38%)を凍結乾燥により水分を除去し、AOS-2を得た。AOS-2中、水分含有量は0質量%、炭素数14及び16のアルファオレフィンスルホン酸ナトリウムの含有量は94.8質量%であった。
表1に示す組成にしたがって、製造例1及び2により得られた内部オレフィンスルホン酸塩(成分(A))、アルファオレフィンスルホン酸塩(成分(B))、及び精製水を用い、これらを80℃で均一に混合し、密閉容器に入れ恒温槽(80℃)にて1晩静置した。次いで、50℃以上で撹拌し、得られた各界面活性剤組成物を3本の50mL遠沈管にそれぞれ20gずつ収容した。
各遠沈管を40℃、25℃、及び15℃に1日保存し、下記方法にしたがって流動性を評価するとともに粘度を測定し、保存安定性の評価も行った。
測定した各界面活性剤組成物の評価結果も含め、結果を表1に示す。
25℃に保存した界面活性剤組成物を「日立高速冷却遠心機 CR21GIII」(日立工機社製、ローターNo.:R15A)用い、25℃、5000r/min、3分の条件にて、遠心脱泡を行った。脱泡された界面活性剤組成物が収容された遠沈管を横向きに数分間静置した後、直ちに遠沈管を立て、そのときの遠沈管内での界面活性剤組成物の流動の有無を目視にて観察し、下記基準にしたがって評価した。
A:界面活性剤組成物の流動が認められる(流動性あり)
B:界面活性剤組成物の流動が認められない(流動性なし)
遠沈管に収容された各界面活性剤組成物について、上記流動性を評価した後、ヘリカル型粘度計「VHS-1」(東機産業(株)製、ローターNo.:T-D)を用い、25℃、5.0r/minの条件にて粘度(Pa・s)を測定した。
遠心による加速試験方法にしたがい、上記遠沈管に収容された各界面活性剤組成物を用い、40℃、25℃、及び15℃の温度域での各界面活性剤組成物の保存安定性の評価を行った。
40℃での保存品として、遠心機「MODEL SL-IVDH」(佐久間製作所製、ローターNo.:BT-1)を用い、槽内温度を40℃に設定し、上記遠沈管を5000r/minにて遠心処理したものを用いた。保存期間が1ヶ月、3ヶ月、及び6ヶ月となる換算遠心時間に相当する10分(1ヶ月に相当)、30分(3ヶ月に相当)、及び60分(6ヶ月に相当)経過した時点での保存品について、下記基準にしたがって目視により評価を行った。
さらに15℃での保存品としては、槽内温度を15℃に設定する以外、25℃での保存品と同様に処理したものを用い、同様にして評価を行った。
A:保存6ヶ月相当の遠心後も均一であり、相分離や析出が認められない。
B:保存3ヶ月相当の遠心後は均一であるが、保存6ヶ月相当では相分離又は析出が認められる。
C:保存1ヶ月相当の遠心後は均一であるが、保存3ヶ月相当では相分離又は析出が認められる。
D:保存1ヶ月相当の遠心後に相分離又は析出が認められる。
実施例7で得られた界面活性剤組成物を用い、下記組成のヘアシャンプーを常法にしたがって調製した。
具体的には、ビーカーに精製水を取り、カチオン化グアーガムを加えて均一に分散させた後、80℃に加温し、実施例7で得られた界面活性剤組成物、ヤシ油脂肪酸アミドプロピルベタイン、ヤシ油脂肪酸モノエタノールアミド、安息香酸ナトリウムを加え、均一に混合した。その後、40℃まで冷却し、エチレングルコールジステアレートを均一に分散させ、香料を加えた。混合時に揮発した水分を調製し、下記組成のヘアシャンプーを得た。
実施例7で得られた界面活性剤組成物 20.0
ヤシ油脂肪酸アミドプロピルベタイン 1.4
ヤシ油脂肪酸モノエタノールアミド 0.6
カチオン化グアーガム ※1 0.3
エチレングリコールジステアレート ※2 5.0
安息香酸ナトリウム 0.3
香料 0.4
精製水 72.0
計 100.0
※2:花王(株)製、「パールコンセントレートFC-1」(エチレングリコールジステアレートとして20%含有)
Claims (16)
- 次の成分(A)、(B)、及び(C):
(A)炭素数16以上18以下の内部オレフィンスルホン酸塩 45.0質量%以上70.0質量%以下、
(B)炭素数12以上14以下のアルファオレフィンスルホン酸塩 0.5質量%以上25.0質量%以下、及び
(C)水
を含有し、かつ成分(A)及び成分(B)の合計含有量が、66.0質量%以上71.0質量%以下である界面活性剤組成物。 - 成分(A)の含有量と成分(B)の含有量との質量比((A)/(B))が、1.8以上140以下である請求項1に記載の界面活性剤組成物。
- 25℃における粘度が、5Pa・s以上155Pa・s以下である、請求項1又は2に記載の界面活性剤組成物。
- 成分(A)中における、炭素数16の内部オレフィンスルホン酸塩の含有量と炭素数18の内部オレフィンスルホン酸塩の含有量との質量比(炭素数16の内部オレフィンスルホン酸塩/炭素数18の内部オレフィンスルホン酸塩)が、100/0~40/60である請求項1~3のいずれか1項に記載の界面活性剤組成物。
- 成分(A)中における、スルホン基が2位に存在する内部オレフィンスルホン酸塩の含有量が、30.0質量%以下である請求項1~4のいずれか1項に記載の界面活性剤組成物。
- 成分(A)中における、内部オレフィンスルホン酸塩のヒドロキシ体の含有量と内部オレフィンスルホン酸塩のオレフィン体の含有量との質量比(ヒドロキシ体/オレフィン体)が、50/50~100/0である請求項1~5のいずれか1項に記載の界面活性剤組成物。
- 成分(A)中における、スルホン酸基の位置がオレフィン鎖又はアルカン鎖の3位から内側に存在するオレフィンスルホン酸塩の含有量が、60.0質量%以上である請求項1~6のいずれか1項に記載の界面活性剤組成物。
- 成分(A)中における、スルホン酸基の位置がオレフィン鎖又はアルカン鎖の1位に存在するオレフィンスルホン酸塩の含有量が、3.0質量%以下である請求項1~7のいずれか1項に記載の界面活性剤組成物。
- 成分(A)及び成分(B)の合計含有量が、69.0質量%以上71.0質量%以下である請求項1~8のいずれか1項に記載の界面活性剤組成物。
- 成分(A)の含有量が、61.0質量%以上69.0質量%以下である請求項1~9のいずれか1項に記載の界面活性剤組成物。
- 成分(B)の含有量が、1.0質量%以上6.0質量%以下である請求項1~10のいずれか1項に記載の界面活性剤組成物。
- 成分(A)の含有量と成分(B)の含有量との質量比((A)/(B))が、2.5以上75.0以下である請求項1~11のいずれか1項に記載の界面活性剤組成物。
- 請求項1~12のいずれか1項記載の界面活性剤組成物の、洗浄剤用基剤としての使用。
- 洗浄剤用基剤が、衣料用洗浄剤用基剤、食器用洗浄剤用基剤、毛髪用洗浄剤用基剤、身体用洗浄剤用基剤、精密部品用洗浄剤用基剤、又は硬質表面用洗浄剤用基剤である請求項13に記載の使用。
- 請求項1~12のいずれか1項記載の界面活性剤組成物の、洗浄剤製造のための使用。
- 洗浄剤用基剤が、衣料用洗浄剤用基剤、食器用洗浄剤用基剤、毛髪用洗浄剤用基剤、身体用洗浄剤用基剤、精密部品用洗浄剤用基剤、又は硬質表面用洗浄剤用基剤である請求項15に記載の使用。
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WO2022071451A1 (ja) | 2020-10-02 | 2022-04-07 | 花王株式会社 | α-アミラーゼ変異体 |
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WO2023120594A1 (ja) | 2021-12-24 | 2023-06-29 | 花王株式会社 | アミラーゼ配合洗浄剤組成物 |
WO2023176970A1 (ja) | 2022-03-18 | 2023-09-21 | 花王株式会社 | α-アミラーゼ変異体 |
WO2023190938A1 (ja) | 2022-03-31 | 2023-10-05 | 花王株式会社 | α-アミラーゼ変異体 |
WO2023199946A1 (ja) | 2022-04-13 | 2023-10-19 | 花王株式会社 | 新規リパーゼ |
WO2023199945A1 (ja) | 2022-04-13 | 2023-10-19 | 花王株式会社 | 新規リパーゼ |
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KR20180091856A (ko) | 2018-08-16 |
BR112018011701A2 (ja) | 2018-12-04 |
CN108368454A (zh) | 2018-08-03 |
EP3388505A1 (en) | 2018-10-17 |
EP3388505B1 (en) | 2020-04-01 |
CN108368454B (zh) | 2020-11-10 |
EP3388505A4 (en) | 2019-06-12 |
JPWO2017098637A1 (ja) | 2017-12-07 |
US20180353411A1 (en) | 2018-12-13 |
JP5973112B1 (ja) | 2016-08-23 |
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