JP5912899B2 - Method for producing anionic surfactant composition - Google Patents
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- JP5912899B2 JP5912899B2 JP2012137527A JP2012137527A JP5912899B2 JP 5912899 B2 JP5912899 B2 JP 5912899B2 JP 2012137527 A JP2012137527 A JP 2012137527A JP 2012137527 A JP2012137527 A JP 2012137527A JP 5912899 B2 JP5912899 B2 JP 5912899B2
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- 239000000203 mixture Substances 0.000 title claims description 51
- 239000003945 anionic surfactant Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- -1 propyleneoxy group Chemical group 0.000 claims description 36
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 19
- 238000005670 sulfation reaction Methods 0.000 claims description 15
- 230000019635 sulfation Effects 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 230000001180 sulfating effect Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920001451 polypropylene glycol Polymers 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 4
- IDEYZABHVQLHAF-GQCTYLIASA-N (e)-2-methylpent-2-enal Chemical compound CC\C=C(/C)C=O IDEYZABHVQLHAF-GQCTYLIASA-N 0.000 description 3
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 description 3
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 2
- AWBIJARKDOFDAN-UHFFFAOYSA-N 2,5-dimethyl-1,4-dioxane Chemical compound CC1COC(C)CO1 AWBIJARKDOFDAN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- BSDORLCHFMTALP-UHFFFAOYSA-N dipropoxy sulfate Chemical compound CCCOOS(=O)(=O)OOCCC BSDORLCHFMTALP-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GSPKZYJPUDYKPI-UHFFFAOYSA-N diethoxy sulfate Chemical compound CCOOS(=O)(=O)OOCC GSPKZYJPUDYKPI-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical class CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XDLVYYYGCNMREZ-UHFFFAOYSA-N propane-1,2-diol;sulfuric acid Chemical compound CC(O)CO.OS(O)(=O)=O XDLVYYYGCNMREZ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ポリオキシプロピレンアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物の製造方法に関する。 The present invention relates to a method for producing an anionic surfactant composition containing a polyoxypropylene alkyl or alkenyl ether sulfate salt.
高級アルコールのアルキレンオキシド付加体（オキシアルキレンアルキルエーテル）の硫酸化により得られるアルキルエーテル硫酸エステル塩は、皮膚に対する刺激が少なく、液体洗浄剤、例えば、シャンプー、医薬、化粧品用のアニオン界面活性剤として広く使用されている。 Alkyl ether sulfates obtained by sulfation of alkylene oxide adducts of higher alcohols (oxyalkylene alkyl ethers) are less irritating to the skin and are used as liquid detergents such as shampoos, pharmaceuticals, and anionic surfactants for cosmetics. Widely used.
一般に、アルキルエーテル硫酸エステル塩は、アルコキシレート化合物にＳＯ3ガスを反応させて硫酸化し、得られた硫酸化物を中和して得られている。ＳＯ3ガスによる原料化合物であるアルコキシレート化合物の硫酸化は高度な発熱を伴う反応である。生成した硫酸化物は熱安定性に乏しく、反応温度に制約がある。よって硫酸化反応生成物は可能な限り冷却することが望ましい。しかしながら硫酸化物は低温では粘稠性で流動性に欠けるため、ＳＯ3ガスとの接触時間増加に伴いしばしば反応物の着色、オーバーリアクションによる分解、炭化物や環化物等に由来する匂いを与える物質の生成などという欠点がある。さらに、流動性が悪いと生産性の低下や設備への負担などをもたらす。そのため、アルキルエーテル硫酸エステル塩の流動性、色相、匂いを改善するために多くの方法が、従来、種々提案されている。 In general, an alkyl ether sulfate salt is obtained by reacting an alkoxylate compound with SO 3 gas for sulfation, and neutralizing the resulting sulfate. Sulfation of an alkoxylate compound, which is a raw material compound with SO 3 gas, is a reaction accompanied by a high exotherm. The produced sulfate has poor thermal stability and the reaction temperature is limited. Therefore, it is desirable to cool the sulfated reaction product as much as possible. However, since sulfur oxide is viscous and lacks fluidity at low temperatures, it is often a substance that gives an odor derived from coloring of reactants, decomposition by overreaction, carbides, cyclized products, etc. as the contact time with SO 3 gas increases. There are drawbacks such as generation. Furthermore, poor fluidity results in reduced productivity and burden on equipment. Therefore, various methods have been proposed in the past for improving the fluidity, hue, and odor of alkyl ether sulfate salts.
特許文献１には、アルキレングリコール硫酸エステルの塩を少なくとも１種含む、流動性のよい高濃度アニオン界面活性剤組成物を、生産性よく製造する方法として、水及び／又はアルキレングリコールと、触媒の存在下、炭素数２〜４のアルキレンオキシドを接触させて所定のエーテル化合物を含む混合物を得、これを硫酸化し、次いで、中和処理する方法が開示されている。 Patent Document 1 discloses, as a method for producing a highly flowable high-concentration anionic surfactant composition containing at least one alkylene glycol sulfate salt with good productivity, water and / or alkylene glycol, and catalyst. A method is disclosed in which an alkylene oxide having 2 to 4 carbon atoms is contacted in the presence to obtain a mixture containing a predetermined ether compound, which is sulfated and then neutralized.
また、特許文献２には、オキシプロピレン基を含む硫酸エステル塩の色相や匂いを改善する方法として、２つ以上の温度制御できるジャケット内に配置された反応管を特定条件で用いた硫酸エステル塩の製造方法が記載されている。 Further, in Patent Document 2, as a method for improving the hue and smell of a sulfate ester salt containing an oxypropylene group, a sulfate ester salt using reaction tubes arranged in two or more temperature-controllable jackets under specific conditions. The manufacturing method is described.
また、特許文献３、４には、エチレンオキサイド付加型のエトキシサルフェートに関して、臭気を改良するために、硫酸化に供せられるエトキシレートに、予め特定のヒドロキシ化合物や水を添加する方法が記載されている。 Patent Documents 3 and 4 describe a method in which a specific hydroxy compound or water is added in advance to an ethoxylate to be subjected to sulfation in order to improve odor with respect to an ethylene oxide addition type ethoxy sulfate. ing.
ポリオキシアルキレンアルキル又はアルケニルエーテル硫酸エステル塩のうち、高級アルコールのプロピレンオキサイド付加体の硫酸化により得られる、ポリオキシプロピレンアルキル又はアルケニルエーテル硫酸エステル塩については、更なる流動性の向上や臭いの低減が望まれる。上記特許文献１においては臭いに関する記載が無いだけでなく、特許文献３、４を含めたこれらの対象物は実質的にプロポキシサルフェートほど臭いが問題視されないエトキシサルフェートであった。また特許文献２は限定された硫酸化設備、および反応条件であり、簡便かつ汎用的に、流動性やにおい品質が良好なポリオキシプロピレンアルキル又はアルケニルエーテル硫酸エステル塩を得るための方法が望まれていた。 Among polyoxyalkylene alkyl or alkenyl ether sulfates, polyoxypropylene alkyl or alkenyl ether sulfates obtained by sulfation of propylene oxide adducts of higher alcohols will further improve fluidity and reduce odor. Is desired. The above-mentioned Patent Document 1 not only has no description about odor, but these objects including Patent Documents 3 and 4 were ethoxy sulfates that have substantially no odor as problematic as propoxysulfate. Patent Document 2 is a limited sulfation facility and reaction conditions, and a method for obtaining a polyoxypropylene alkyl or alkenyl ether sulfate ester salt having good fluidity and odor quality in a simple and versatile manner is desired. It was.
本発明は、流動性が良好で臭いが改善された、アルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物の製造方法に関する。 The present invention relates to a method for producing an anionic surfactant composition containing an alkyl or alkenyl ether sulfate having good flowability and improved odor.
本発明は、下記工程（Ａ）、（Ｂ）及び（Ｃ）を有する、一般式３で表される化合物を含有するアニオン界面活性剤組成物の製造方法に関する。
工程（Ａ）：一般式１で表される化合物、一般式２で表される化合物、及び水を含有し、水の含有量が０．２質量％以上、０．８質量％以下である原料混合物に、プロピレンオキサイドを付加させて反応生成物を得る工程
工程（Ｂ）：工程（Ａ）で得られた反応生成物を硫酸化する工程
工程（Ｃ）：工程（Ｂ）で得られた硫酸化物を中和する工程
ＲＯＨ …１
式中、Ｒは炭素数８以上、２４以下のアルキル基又はアルケニル基を示す。
Ｍ（ＯＨ）z …２
式中、Ｍはアルカリ金属又はアルカリ土類金属を示す。ＺはＭがアルカリ金属の場合は１、アルカリ土類金属の場合は２である。
ＲＯ（ＰＯ）nＳＯ3Ｍ1 …３
式中、Ｒは炭素数８以上、２４以下のアルキル基又はアルケニル基を示し、ＰＯはプロピレンオキシ基を示し、ｎはＰＯの平均付加モル数を示す０超、１０以下の数であり、Ｍ1は陽イオン基を示す。
This invention relates to the manufacturing method of the anionic surfactant composition containing the compound represented by General formula 3 which has the following process (A), (B) and (C).
Process (A): The raw material which contains the compound represented by General formula 1, the compound represented by General formula 2, and water and whose water content is 0.2 mass% or more and 0.8 mass% or less. Step (B) for obtaining a reaction product by adding propylene oxide to the mixture: Step (C) for sulfating the reaction product obtained in step (A) Step (C): sulfuric acid obtained in step (B) Step of neutralizing compound ROH 1
In the formula, R represents an alkyl group or an alkenyl group having 8 to 24 carbon atoms.
M (OH) z 2
In the formula, M represents an alkali metal or an alkaline earth metal. Z is 1 when M is an alkali metal, and 2 when M is an alkaline earth metal.
RO (PO) n SO 3 M 1 … 3
In the formula, R represents an alkyl group or alkenyl group having 8 or more and 24 or less carbon atoms, PO represents a propyleneoxy group, n represents an average added mole number of PO, a number of more than 0 and 10 or less, M 1 represents a cationic group.
本発明によれば、流動性が良好で臭いが改善されたプロピレンオキサイド付加型のアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the anionic surfactant composition containing the propylene oxide addition-type alkyl or alkenyl ether sulfate ester salt with favorable fluidity | liquidity and improved odor is provided.
＜工程（Ａ）＞
一般式１で表される化合物、一般式２で表される化合物、及び水を含有し、水の含有量が０．２質量％以上、０．８質量％以下である原料混合物に、プロピレンオキサイドを付加させて反応生成物を得る。
<Process (A)>
Propylene oxide is added to the raw material mixture containing the compound represented by the general formula 1, the compound represented by the general formula 2, and water, and the water content is 0.2% by mass or more and 0.8% by mass or less. To obtain a reaction product.
一般式１で表される化合物のＲは、最終的な界面活性剤の用途などを考慮して適宜選定できるが、洗浄性、取り扱い性の観点から、炭素数８以上であり、そして、炭素数１８以下、更に１６以下、更に１４以下が好ましい。 R of the compound represented by the general formula 1 can be appropriately selected in consideration of the final use of the surfactant, etc., but from the viewpoint of detergency and handleability, R is 8 or more, and the carbon number It is preferably 18 or less, more preferably 16 or less, and further 14 or less.
一般式２で表される化合物は、触媒であり、Ｍはナトリウム、カリウムなどのアルカリ金属、カルシウム、バリウムなどのアルカリ土類金属が挙げられ、アルカリ金属が好ましい。一般式２で表される化合物は、水酸化ナトリウム、及び水酸化カリウムから選ばれる化合物が好ましく、水酸化カリウムがより好ましい。 The compound represented by the general formula 2 is a catalyst, and M is an alkali metal such as sodium or potassium, or an alkaline earth metal such as calcium or barium, and an alkali metal is preferable. The compound represented by Formula 2 is preferably a compound selected from sodium hydroxide and potassium hydroxide, more preferably potassium hydroxide.
工程（Ａ）の原料混合物中の一般式１で表される化合物の含有量は、９５．０質量％以上、更に９６．０質量％以上、更に９７．０質量％以上、更に９８．０質量％以上が好ましく、そして、９９．８質量％以下、更に９９．７質量％以下、更に９９．６質量％以下、更に９９．５質量％以下が好ましい。 The content of the compound represented by the general formula 1 in the raw material mixture in the step (A) is 95.0% by mass or more, further 96.0% by mass or more, further 97.0% by mass or more, and further 98.0% by mass. % Or more, and 99.8% by mass or less, more preferably 99.7% by mass or less, further 99.6% by mass or less, and further preferably 99.5% by mass or less.
工程（Ａ）の原料混合物中の一般式２で表される化合物の含有量は、０．０１質量％以上、更に０．０２質量％以上、更に０．０３質量％以上、更に０．０４質量％以上が好ましく、そして、４．０質量％以下、更に３．０質量％以下、更に２．０質量％以下、更に１．０質量％以下が好ましい。 The content of the compound represented by the general formula 2 in the raw material mixture in the step (A) is 0.01% by mass or more, further 0.02% by mass or more, further 0.03% by mass or more, and further 0.04% by mass. % Or more, and 4.0% by mass or less, further 3.0% by mass or less, further 2.0% by mass or less, and further preferably 1.0% by mass or less.
工程（Ａ）の原料混合物中の水の含有量は、０．２質量％以上、０．８質量％以下であり、０．２５質量％以上、更に０．３０質量％以上、更に０．３５質量％以上、更に０．４０質量％以上が好ましく、そして、０．７５質量％以下、更に０．７０質量％以下、更に０．６５質量％以下、更に０．６０質量％以下が好ましい。プロピレンオキサイドを付加する前の段階で原料混合物中の水の含有量をこの範囲とすることで、洗浄性や起泡性などの洗浄基剤としての性質を維持しつつ、流動性が良好で、臭いが改善された、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物が得られる。 The content of water in the raw material mixture in the step (A) is 0.2% by mass or more and 0.8% by mass or less, 0.25% by mass or more, further 0.30% by mass or more, and further 0.35%. It is preferably at least 0.4% by mass, more preferably at least 0.40% by mass, and further preferably at most 0.75% by mass, further at most 0.70% by mass, further at most 0.65% by mass and at most 0.60% by mass. By making the content of water in the raw material mixture in this range before adding propylene oxide within this range, while maintaining the properties as a cleaning base such as detergency and foaming properties, fluidity is good, An anionic surfactant composition containing an alkyl or alkenyl ether sulfate represented by the general formula 3 and having improved odor is obtained.
水の含有量が前記範囲にある原料混合物に対して、プロピレンオキサイドを付加させて、一般式１で表される化合物のプロピレンオキサイド付加物であるポリオキシプロピレンアルキル又はアルケニルエーテルを含む反応生成物を得る。この反応生成物を硫酸化後、中和して得られる界面活性剤の洗浄性能の観点から、プロピレンオキサイドは、一般式１で表される化合物１モルに対して、０モル超、そして、１０モル以下、更に５モル以下、更に２モル以下で付加することが好ましい。 A reaction product containing polyoxypropylene alkyl or alkenyl ether, which is a propylene oxide adduct of a compound represented by the general formula 1, by adding propylene oxide to a raw material mixture having a water content in the above range. obtain. From the viewpoint of the washing performance of the surfactant obtained by sulfating and neutralizing the reaction product, propylene oxide is more than 0 mol per mol of the compound represented by the general formula 1 and 10 mol. It is preferable to add at a mole or less, further 5 moles or less, and further 2 moles or less.
また、工程（Ａ）で得られた反応生成物中のプロピレンオキサイドの含有量は、硫酸化物の臭気の観点から、１５０ｍｇ／ｋｇ以下、更に１３０ｍｇ／ｋｇ以下、更に１２０ｍｇ／ｋｇ以下、更に１１０ｍｇ／ｋｇ以下、更に１００ｍｇ／ｋｇ以下が好ましい。当該反応生成物中のプロピレンオキサイドの含有量は、プロピレンオキサイド反応前の原料混合物中の水分を制御することにより調整できる。 In addition, the content of propylene oxide in the reaction product obtained in the step (A) is 150 mg / kg or less, further 130 mg / kg or less, further 120 mg / kg or less, further 110 mg / kg from the viewpoint of the odor of sulfate. kg or less, more preferably 100 mg / kg or less. The content of propylene oxide in the reaction product can be adjusted by controlling the moisture in the raw material mixture before the propylene oxide reaction.
＜工程（Ｂ）＞
工程（Ｂ）では、工程（Ａ）で得られた反応生成物を硫酸化する。工程（Ｂ）では、一般式１で表される化合物のプロピレンオキサイド付加物の硫酸化物などを含む硫酸化物が得られる。
<Process (B)>
In the step (B), the reaction product obtained in the step (A) is sulfated. In the step (B), a sulfate containing a propylene oxide adduct of the compound represented by the general formula 1 is obtained.
硫酸化には、硫酸化剤が用いられる。硫酸化剤としては、アニオン界面活性剤組成物中の無機塩量をできるだけ少なくするために、ガス状三酸化硫黄を用いることが好ましい。硫酸化の方法に特に制限はなく、常法にしたがって行うことができる。例えば、空気や窒素などの不活性ガスで希釈した、好ましくは濃度１容量％以上、また、３０容量％以下、更に２０容量％以下のガス状三酸化硫黄を、工程（Ａ）で得られた反応生成物に接触させることで硫酸化を行う。三酸化硫黄の濃度が１〜３０容量％の範囲であればガス容積が大きすぎることなく、また反応が過剰になるのを抑制することができる。 A sulfating agent is used for the sulfation. As the sulfating agent, gaseous sulfur trioxide is preferably used in order to minimize the amount of inorganic salt in the anionic surfactant composition. There is no restriction | limiting in particular in the method of sulfation, It can carry out according to a conventional method. For example, gaseous sulfur trioxide diluted with an inert gas such as air or nitrogen, preferably having a concentration of 1% by volume or more, 30% by volume or less, and further 20% by volume or less was obtained in the step (A). Sulfation is carried out by contact with the reaction product. If the concentration of sulfur trioxide is in the range of 1 to 30% by volume, the gas volume is not too large and the reaction can be prevented from becoming excessive.
三酸化硫黄の使用量は、通常、化学量論量×（０．９５〜１．０５）の範囲である。該三酸化硫黄の使用量が上記範囲であれば、起泡性に乏しい未反応ポリオキシプロピレンアルキル又はアルケニルエーテル、ポリプロピレングリコール、プロピレングリコール硫酸エステル、ポリプロピレングリコール硫酸エステルなどの量が少なく、かつ副生物である有臭成分（例えば低級アルデヒド、低級ケトン、環状エーテルなど）の生成量も少ない。好ましい量は、化学量論量×（０．９７〜１．０１）の範囲である。 The amount of sulfur trioxide used is usually in the range of stoichiometric amount × (0.95 to 1.05). If the amount of sulfur trioxide used is in the above range, the amount of unreacted polyoxypropylene alkyl or alkenyl ether, polypropylene glycol, propylene glycol sulfate, polypropylene glycol sulfate, etc. with poor foaming properties is small, and by-products The amount of odorous components (for example, lower aldehydes, lower ketones, cyclic ethers, etc.) produced is also small. A preferred amount is in the range of stoichiometric amount × (0.97 to 1.01).
硫酸化を行う反応装置に制限はなく、例えば槽型反応装置や薄膜式反応装置などを用いることができる。薄膜式反応装置としては、例えば流下薄膜式反応装置、上昇薄膜型反応装置及び管型気液混合相流反応装置などを用いることができる。製造効率の観点からは、薄膜式反応装置、更に薄膜式反応装置による連続式を適用することが好ましい。この薄膜式反応装置の中でも、反応効率及び着色などの観点から、流下薄膜式反応装置が好ましい。薄膜式反応装置を用いた場合の反応時間は、１０〜３００秒間程度である。 There is no restriction | limiting in the reactor which performs sulfation, For example, a tank reactor, a thin film reactor, etc. can be used. As the thin film reactor, for example, a falling thin film reactor, a rising thin film reactor, a tubular gas-liquid mixed phase flow reactor, and the like can be used. From the viewpoint of production efficiency, it is preferable to apply a thin film reactor, and further a continuous system using a thin film reactor. Among these thin film reactors, a falling film reactor is preferable from the viewpoint of reaction efficiency and coloring. The reaction time when using a thin film reactor is about 10 to 300 seconds.
硫酸化温度は、好ましくは１５℃以上、更に４０℃以上、また、７０℃以下、更に６０℃以下である。１５℃以上であれば流動性低下による局部的な反応過剰を抑制することができ、また７０℃以下であれば生成物の分解を抑制することができる。 The sulfation temperature is preferably 15 ° C. or higher, further 40 ° C. or higher, 70 ° C. or lower, and further 60 ° C. or lower. If it is 15 degreeC or more, the local excessive reaction by fluidity | liquidity fall can be suppressed, and if it is 70 degrees C or less, decomposition | disassembly of a product can be suppressed.
＜工程（Ｃ）＞
工程（Ｃ）では、工程（Ｂ）で得られた硫酸化物を中和する。これにより、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物が得られる。一般式３中のｎは、０超、１０以下の数である。ｎは、５以下、更に２以下の数が好ましい。一般式３で表される化合物のＲは、一般式１に対応したものとなる。一般式３中のＲも、洗浄性、取り扱い性の観点から、炭素数８以上であり、そして、炭素数１８以下、更に１６以下、更に１４以下が好ましい。
<Process (C)>
In the step (C), the sulfate obtained in the step (B) is neutralized. Thereby, the anionic surfactant composition containing the alkyl or alkenyl ether sulfate represented by the general formula 3 is obtained. N in General Formula 3 is a number greater than 0 and 10 or less. n is preferably 5 or less, more preferably 2 or less. R of the compound represented by the general formula 3 corresponds to the general formula 1. R in the general formula 3 also has 8 or more carbon atoms from the viewpoint of detergency and handleability, and preferably 18 or less, more preferably 16 or less, and further 14 or less.
中和は、好ましくは硫酸化反応の直後に行なう。中和温度は、２０℃以上、更に２５℃以上、また、６０℃以下、更に５０℃以下が好ましい。 Neutralization is preferably performed immediately after the sulfation reaction. The neutralization temperature is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, 60 ° C. or lower, and further preferably 50 ° C. or lower.
中和は塩基性中和剤を用いて行われる。塩基性中和剤としては、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アンモニア、炭素数２〜３のアルカノール基を有するモノ、ジもしくはトリアルカノールアミンである。水酸化カリウム、水酸化ナトリウム、アンモニア、モノエタノールアミン、及びトリエタノールアミンから選ばれる塩基性中和剤を好適に使用することができる。 Neutralization is performed using a basic neutralizing agent. Examples of the basic neutralizing agent include alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, and mono-, di- or trialkanol amines having an alkanol group having 2 to 3 carbon atoms. A basic neutralizing agent selected from potassium hydroxide, sodium hydroxide, ammonia, monoethanolamine, and triethanolamine can be preferably used.
また、中和後の混合物は、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物であり、通常、有効分である一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩の濃度が２０質量％以上のペースト状組成物であり、有効分濃度は適宜調整できる。本発明では、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩の濃度が５５質量％以上、更に６０質量％以上、更に６５質量％以上、そして、８５質量％以下、更に８０質量％以下、更に７５質量％以下のアニオン界面活性剤組成物を得ることができる。 Moreover, the mixture after neutralization is an anionic surfactant composition containing an alkyl or alkenyl ether sulfate ester salt represented by general formula 3, and is usually an alkyl or alkenyl ether represented by general formula 3 which is an effective component. The concentration of the alkenyl ether sulfate ester salt is 20% by mass or more, and the effective concentration can be appropriately adjusted. In the present invention, the concentration of the alkyl or alkenyl ether sulfate represented by the general formula 3 is 55% by mass or more, further 60% by mass or more, further 65% by mass or more, and 85% by mass or less, and further 80% by mass or less. Furthermore, an anionic surfactant composition of 75% by mass or less can be obtained.
このようにして、少なくとも、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物が得られる。本発明の方法により製造されたアニオン界面活性剤組成物は、一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩を高濃度で含有していても流動性が良好で取扱い性がよく、また、臭いも改善されている。 In this way, an anionic surfactant composition containing at least an alkyl or alkenyl ether sulfate represented by the general formula 3 is obtained. The anionic surfactant composition produced by the method of the present invention has good flowability and good handleability even when it contains an alkyl or alkenyl ether sulfate ester salt represented by the general formula 3 at a high concentration. The odor has also been improved.
特許文献２でも言及しているように、オキシプロピレン基を含む硫酸エステル塩は、オキシエチレン基のみを含む硫酸エステル塩のような対処方法では、臭気の問題を十分に解決することができない。すなわち、硫酸化反応時に未反応のプロピレンオキサイドを由来としてにおい物質が副生し、硫酸化物の臭気が悪化する。そのため、硫酸化原料中の未反応プロピレンオキサイドを可能な限り低減することが、におい品質の面から望ましい。その際、プロピレンオキサイド付加反応系中の水分量が多いほど、未反応プロピレンオキサイドは低減されるが、副生するポリプロピレングリコール量は増加する。そのような反応生成物を工程（Ｂ）で用いると、得られる硫酸化物中のポリプロピレングリコール硫酸化物の含有量が多くなりすぎて、目的とするアニオン界面活性剤組成物の洗浄性や起泡性などの洗浄基剤としての性質に悪影響を及ぼすおそれがある。 As mentioned in Patent Document 2, a sulfate ester salt containing an oxypropylene group cannot sufficiently solve the odor problem by a countermeasure such as a sulfate ester salt containing only an oxyethylene group. That is, an unreacted propylene oxide is derived as a by-product from the unreacted propylene oxide during the sulfation reaction, and the odor of the sulfate is deteriorated. Therefore, it is desirable from the aspect of odor quality to reduce unreacted propylene oxide in the sulfated raw material as much as possible. At that time, as the amount of water in the propylene oxide addition reaction system increases, the amount of unreacted propylene oxide decreases, but the amount of by-produced polypropylene glycol increases. When such a reaction product is used in the step (B), the content of polypropylene glycol sulfate in the obtained sulfate is excessively increased, and the detergency and foamability of the target anionic surfactant composition are increased. It may adversely affect the properties as a cleaning base.
本発明では、プロピレンオキサイドを付加させる前の原料混合物について、水の含有量を所定範囲とする方法により、アニオン界面活性剤組成物の洗浄基剤としての性質を損なわずに、におい品質を向上できることを見出したものである。つまり、プロピレンオキサイド付加反応の系中（原料混合物中）に所定量の水が存在することで、系中の未反応のプロピレンオキサイドの残存量は低減される。その詳細な理由は不明であるが、所定量の水が存在することによって、反応系中にて何らかの活性水素化合物を生成する事で未反応プロピレンオキサイドの残存量が低減されたものと考えられる。未反応のプロピレンオキサイドを低減した原料を使用して得られた硫酸化物は、特許文献２の実施例で測定している２−メチル−２−ペンテナールのようなにおい物質が少なく、良好な臭気が得られる。本発明は、プロピレンオキサイド反応時（工程（Ａ））に反応系中に所定量の水が存在していることがポイントであり、工程（Ａ）でプロピレンオキサイド付加反応系中（原料混合物中）の水分を適正量に管理する必要がある。後述の比較例３のように、プロピレンオキサイド反応終了後に水を加えて、系中の水の量を工程（Ａ）で用いる原料混合物中の量と同程度にした反応生成物を硫酸化したとしても、におい品質、流動性が良好な硫酸化物、更にその中和物を得ることは出来ない。従って、特許文献４をプロポキシサルフェートの製造に適用しても、におい品質、流動性が良好な硫酸化物、更にその中和物を得ることは出来ない。 In the present invention, the raw material mixture before adding propylene oxide can improve the odor quality without impairing the properties as a cleaning base of the anionic surfactant composition by a method of setting the water content within a predetermined range. Is found. That is, the presence of a predetermined amount of water in the propylene oxide addition reaction system (in the raw material mixture) reduces the remaining amount of unreacted propylene oxide in the system. Although the detailed reason is unknown, it is thought that the residual amount of unreacted propylene oxide was reduced by producing some active hydrogen compounds in the reaction system due to the presence of a predetermined amount of water. Sulfur oxide obtained by using raw materials with reduced unreacted propylene oxide has little odorous substance such as 2-methyl-2-pentenal measured in Examples of Patent Document 2, and has a good odor. can get. The point of the present invention is that a predetermined amount of water is present in the reaction system during the propylene oxide reaction (step (A)), and in the propylene oxide addition reaction system (in the raw material mixture) in step (A). It is necessary to manage the amount of water in an appropriate amount. As in Comparative Example 3 described later, water was added after completion of the propylene oxide reaction, and the reaction product in which the amount of water in the system was the same as the amount in the raw material mixture used in step (A) was sulfated. However, it is impossible to obtain a sulfur oxide having good odor quality and fluidity, and further a neutralized product thereof. Therefore, even if Patent Document 4 is applied to the production of propoxy sulfate, it is not possible to obtain a sulfur oxide having good odor quality and fluidity, and further a neutralized product thereof.
本発明の方法により製造されたアニオン界面活性剤組成物は、有効分である一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩の濃度が６５質量％において、温度４０℃における粘度が１００００ｍＰａ・ｓ以下、更に９５００ｍＰａ・ｓ以下、更に９０００ｍＰａ・ｓ以下、更に８０００ｍＰａ・ｓ以下であることが好ましい。 The anionic surfactant composition produced by the method of the present invention has an effective content of an alkyl or alkenyl ether sulfate represented by the general formula 3 of 65% by mass, a viscosity at 40 ° C. of 10,000 mPa · It is preferably s or less, further 9500 mPa · s or less, further 9000 mPa · s or less, and further 8000 mPa · s or less.
本発明の方法で得られたアニオン界面活性剤組成物は、液体洗浄剤組成物に好適に用いることができる。この場合、該液体洗浄剤組成物には、必要に応じて色素、香料、可溶化剤、ビルダーなどの補助剤を適宜加えることができる。さらに、洗浄力や泡立ちを調整する目的で、他のアニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、アミド型非イオン界面活性剤などを添加することができる。液体洗浄剤組成物は、例えば、シャンプー、ボディシャンプー、台所用洗剤、リキッドソープなどに用いられる。 The anionic surfactant composition obtained by the method of the present invention can be suitably used for a liquid detergent composition. In this case, auxiliary agents such as pigments, fragrances, solubilizers, and builders can be appropriately added to the liquid detergent composition as necessary. Furthermore, for the purpose of adjusting detergency and foaming, other anionic surfactants, cationic surfactants, amphoteric surfactants, amide type nonionic surfactants and the like can be added. The liquid detergent composition is used for shampoos, body shampoos, kitchen detergents, liquid soaps, and the like.
下記に実施例を示すが、本発明はこれに限定されるものではない。 Examples are shown below, but the present invention is not limited thereto.
表１の原料混合物から以下の方法でアニオン界面活性剤組成物を製造し、以下の評価を行った。結果を表１に示す。なお、実施例１〜５、比較例１〜３の工程（Ａ）は、それぞれ、以下のようにして行った。 An anionic surfactant composition was produced from the raw material mixture of Table 1 by the following method, and the following evaluation was performed. The results are shown in Table 1. In addition, the process (A) of Examples 1-5 and Comparative Examples 1-3 was performed as follows, respectively.
〔１〕アニオン界面活性剤組成物の製造
＜工程（Ａ）＞
〔実施例１〜５〕
表１に示す構造、仕込量で、一般式１の化合物と一般式２の化合物、および水を攪拌装置、温度制御装置、自動導入装置を備えたオートクレーブに仕込み、窒素置換を行い、１２５℃まで昇温した後、プロピレンオキサイドを、一般式１の化合物に対する平均付加モル数が表１中の値となるような量で仕込んだ。１２５℃にて付加反応・熟成を行った後、８０℃まで冷却し、９０％乳酸をオートクレーブ内に加え、８０℃で３０分間攪拌した後、抜き出しを行い、ポリオキシプロピレンアルキルエーテルを含有する反応生成物を得た。
[1] Production of anionic surfactant composition <Step (A)>
[Examples 1 to 5]
With the structure and charge shown in Table 1, the compound of general formula 1 and the compound of general formula 2 and water were charged into an autoclave equipped with a stirrer, temperature controller, and automatic introduction device, and nitrogen substitution was performed up to 125 ° C. After raising the temperature, propylene oxide was charged in an amount such that the average number of moles added relative to the compound of general formula 1 was the value shown in Table 1. After addition reaction and ripening at 125 ° C, cooling to 80 ° C, adding 90% lactic acid into the autoclave, stirring at 80 ° C for 30 minutes, then drawing out and containing polyoxypropylene alkyl ether The product was obtained.
〔比較例１〕
表１に示す構造、仕込量で、一般式１の化合物と一般式２の化合物を攪拌装置、温度制御装置、自動導入装置を備えたオートクレーブに仕込み、１１０℃、１．３ｋＰａにて３０分間脱水を行った。脱水後、窒素置換を行い、実施例１〜５と同様の方法でプロピレンオキサイドを反応させて反応生成物を得た。
[Comparative Example 1]
Charge the compound of general formula 1 and the compound of general formula 2 into the autoclave equipped with a stirrer, temperature controller and automatic introduction device with the structure and charge shown in Table 1 and dehydrate at 110 ° C. and 1.3 kPa for 30 minutes. Went. After dehydration, nitrogen substitution was performed, and propylene oxide was reacted in the same manner as in Examples 1 to 5 to obtain a reaction product.
〔比較例２〕
表１に示す構造、仕込量で、一般式１の化合物と一般式２の化合物、およびプロピレングリコールを攪拌装置、温度制御装置、自動導入装置を備えたオートクレーブに仕込み、実施例１〜５と同様の方法でプロピレンオキサイドを反応させて反応生成物を得た。
[Comparative Example 2]
In the structure and charge shown in Table 1, the compound of general formula 1, the compound of general formula 2, and propylene glycol were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, and the same as in Examples 1-5 The reaction product was obtained by reacting propylene oxide by the method described above.
〔比較例３〕
比較例１で得られた反応生成物に表１に示す量で水を添加して工程（Ｂ）に用いる反応生成物を得た。
[Comparative Example 3]
Water was added to the reaction product obtained in Comparative Example 1 in the amount shown in Table 1 to obtain a reaction product used in the step (B).
＜工程（Ｂ）＞
工程（Ａ）で得られた反応生成物を、ＳＯ3ガスを用いて薄膜式硫酸化反応器にて硫酸化した。
<Process (B)>
The reaction product obtained in the step (A) was sulfated in a thin-film sulfation reactor using SO 3 gas.
＜工程（Ｃ）＞
工程（Ｂ）で得られた硫酸化物を水酸化ナトリウム水溶液で中和し、ポリオキシプロピレンアルキルエーテル硫酸エステル塩を含有するアニオン界面活性剤組成物を得た。
<Process (C)>
The sulfate obtained in the step (B) was neutralized with an aqueous sodium hydroxide solution to obtain an anionic surfactant composition containing a polyoxypropylene alkyl ether sulfate ester salt.
〔２〕評価
（２−１）ジメチルジオキサン及び２−メチル２−ペンテナール含有量
アニオン界面活性剤組成物中のジメチルジオキサン含有量及び２−メチル２−ペンテナール含有量を、以下の機器から構成されるヘッドスペースガスクロマトグラフィーにより測定した。
・ヘッドスペースユニット：Agilent Technologies社製、Ｇ１８８８
・ガスクロマトグラフ：Agilent Technologies社製、７８９０Ａ
・検出器：Agilent Technologies社製、５９７５Ｃ
[2] Evaluation (2-1) Dimethyldioxane and 2-methyl 2-pentenal content The dimethyldioxane content and 2-methyl 2-pentenal content in the anionic surfactant composition are composed of the following equipment. Measured by headspace gas chromatography.
-Headspace unit: G1888, manufactured by Agilent Technologies
Gas chromatograph: 7890A manufactured by Agilent Technologies
Detector: Agilent Technologies, 5975C
（２−２）臭い
アニオン界面活性剤組成物を蓋付きガラス瓶に入れ、瓶口の臭いをにおい評価パネラーの官能試験により評価し、以下の基準で判定した。
○：無臭か、わずかなグリーン臭、脂肪酸様臭
×：強いグリーン臭、脂肪酸様臭
(2-2) Odor The anionic surfactant composition was put in a glass bottle with a lid, and the odor of the bottle mouth was evaluated by a sensory test of an odor evaluation panel, and judged according to the following criteria.
○: Odorless, slight green odor, fatty acid-like odor ×: Strong green odor, fatty acid-like odor
（２−３）流動性
アニオン界面活性剤組成物中の有効分（一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩）濃度を６５質量％に調整し、４０℃の条件にてＢ型粘度計を使用した粘度により評価した。
(2-3) Fluidity An effective component (alkyl or alkenyl ether sulfate ester salt represented by the general formula 3) in the anionic surfactant composition is adjusted to a concentration of 65% by mass, and the B type is obtained at 40 ° C. The viscosity was evaluated by using a viscometer.
注１）カールフィッシャー法による実測値（原料由来の水分、仕込み水量と生成水の総量から計算した理論量にほぼ等しい）。比較例１〜３では、一般式１の化合物と一般式２の化合物を混合した時点で、プロピレンオキサイドの付加前に、表中の水分量となる。
注２）反応生成物中の水の含有量に換算すると０．５７質量％となる。
注３）工程（Ｃ）で得られた組成物中の一般式３で表されるアルキル又はアルケニルエーテル硫酸エステル塩の濃度
Note 1) Measured value by Karl Fischer method (approximately equal to the theoretical amount calculated from the raw material-derived moisture, the amount of feed water and the total amount of product water). In Comparative Examples 1 to 3, when the compound of the general formula 1 and the compound of the general formula 2 are mixed, before the addition of propylene oxide, the moisture content in the table is obtained.
Note 2) When converted to the content of water in the reaction product, it becomes 0.57% by mass.
Note 3) Concentration of alkyl or alkenyl ether sulfate represented by general formula 3 in the composition obtained in step (C)
表１中、一般式１の化合物のＲは、全て直鎖のアルキル基であり、Ｃの次の数字が炭素数を意味する。例えば、「Ｃ１２」は、炭素数１２の直鎖アルキル基を意味する。また、表１中、「ＰＧ」はプロピレングリコール、「ＰＯ」はプロピレンオキサイド、「反応生成物」は、工程（Ａ）で得られた、ポリオキシプロピレンアルキルエーテルを含有する反応生成物の意味である。 In Table 1, R of the compound of the general formula 1 is a linear alkyl group, and the number after C means the number of carbon atoms. For example, “C12” means a linear alkyl group having 12 carbon atoms. In Table 1, “PG” means propylene glycol, “PO” means propylene oxide, and “reaction product” means a reaction product containing polyoxypropylene alkyl ether obtained in step (A). is there.
Claims (7)
工程（Ａ）：一般式１で表される化合物、一般式２で表される化合物、及び水を含有し、水の含有量が０．２質量％以上、０．８質量％以下である原料混合物に、プロピレンオキサイドを付加させて反応生成物を得る工程
工程（Ｂ）：工程（Ａ）で得られた反応生成物を硫酸化する工程
工程（Ｃ）：工程（Ｂ）で得られた硫酸化物を中和する工程
ＲＯＨ …１
式中、Ｒは炭素数８以上、２４以下のアルキル基又はアルケニル基を示す。
Ｍ（ＯＨ）z …２
式中、Ｍはアルカリ金属又はアルカリ土類金属を示し、ＺはＭがアルカリ金属の場合は１、アルカリ土類金属の場合は２である。
ＲＯ（ＰＯ）nＳＯ3Ｍ1 …３
式中、Ｒは炭素数８以上、２４以下のアルキル基又はアルケニル基を示し、ＰＯはプロピレンオキシ基を示し、ｎはＰＯの平均付加モル数を示す０超、１０以下の数であり、Ｍ1は陽イオン基を示す。 The manufacturing method of the anionic surfactant composition containing the compound represented by General formula 3 which has the following process (A), (B) and (C).
Process (A): The raw material which contains the compound represented by General formula 1, the compound represented by General formula 2, and water and whose water content is 0.2 mass% or more and 0.8 mass% or less. Step (B) for obtaining a reaction product by adding propylene oxide to the mixture: Step (C) for sulfating the reaction product obtained in step (A) Step (C): sulfuric acid obtained in step (B) Step of neutralizing compound ROH 1
In the formula, R represents an alkyl group or an alkenyl group having 8 to 24 carbon atoms.
M (OH) z 2
In the formula, M represents an alkali metal or an alkaline earth metal, and Z is 1 when M is an alkali metal, and 2 when M is an alkaline earth metal.
RO (PO) n SO 3 M 1 … 3
In the formula, R represents an alkyl group or alkenyl group having 8 or more and 24 or less carbon atoms, PO represents a propyleneoxy group, n represents an average added mole number of PO, a number of more than 0 and 10 or less, M 1 represents a cationic group.
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