JP6478310B2 - Reactive surfactant composition - Google Patents
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- JP6478310B2 JP6478310B2 JP2014026946A JP2014026946A JP6478310B2 JP 6478310 B2 JP6478310 B2 JP 6478310B2 JP 2014026946 A JP2014026946 A JP 2014026946A JP 2014026946 A JP2014026946 A JP 2014026946A JP 6478310 B2 JP6478310 B2 JP 6478310B2
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- 239000004094 surface-active agent Substances 0.000 title claims description 95
- 239000000203 mixture Substances 0.000 title claims description 28
- 230000002209 hydrophobic effect Effects 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 125000003827 glycol group Chemical group 0.000 claims description 14
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- 239000002041 carbon nanotube Substances 0.000 description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 229910021382 natural graphite Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
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- 238000003786 synthesis reaction Methods 0.000 description 10
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- -1 diallyl compound Chemical class 0.000 description 8
- 229960003390 magnesium sulfate Drugs 0.000 description 8
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- 235000019341 magnesium sulphate Nutrition 0.000 description 8
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- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 238000001179 sorption measurement Methods 0.000 description 3
- YFFFQGXWMHAJPP-UHFFFAOYSA-N 1-[2-[2-(2-bromoethoxy)ethoxy]ethoxy]-2-methoxyethane Chemical compound COCCOCCOCCOCCBr YFFFQGXWMHAJPP-UHFFFAOYSA-N 0.000 description 2
- PJKNFAICTFGCDT-UHFFFAOYSA-N 2-(2-aminopropan-2-yldiazenyl)propan-2-amine;hydron;dichloride Chemical compound Cl.Cl.CC(C)(N)N=NC(C)(C)N PJKNFAICTFGCDT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical group C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- USEGQJLHQSTGHW-UHFFFAOYSA-N 3-bromo-2-methylprop-1-ene Chemical compound CC(=C)CBr USEGQJLHQSTGHW-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WWSUBBGNJOEZPQ-UHFFFAOYSA-N C(C=C)(=O)CCON Chemical compound C(C=C)(=O)CCON WWSUBBGNJOEZPQ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、特に疎水性物質の乳化分散に使用する場合に、被分散体からの界面活性剤の遊離を防止しつつ、充分な乳化分散を可能とした反応性界面活性剤及び該反応性界面活性剤を用いた反応性界面活性剤組成物に関する。 The present invention relates to a reactive surfactant capable of sufficient emulsification and dispersion while preventing the release of the surfactant from the dispersion, particularly when used for emulsification and dispersion of hydrophobic substances, and the reactive interface. The present invention relates to a reactive surfactant composition using an activator.
界面活性剤は、例えば、塗料、印刷インキ、接着剤等ではその製品の製造時、或いは製品の安定化、更には作業性等の点で欠かすことができない成分として製品中に含有されている。
また、界面活性剤は、乳化重合によってポリマーを製造する際に使用される乳化重合用乳化剤としても用いられ、重合の開始反応や成長反応に関与するだけでなく、生成したエマルジョンの機械安定性、化学的安定性、凍結安定性及び貯蔵安定性等にも関与し、更にエマルジョンの粒子径、粘性及び起泡性等のエマルジョン物性、フィルム化した時の耐水性、耐候性、接着性、耐熱性等のフィルム物性にも大きな影響を及ぼすことが知られている。
The surfactant is contained in the product as a component that is indispensable, for example, in the production of the product in the case of paint, printing ink, adhesive, etc., or in terms of stabilization of the product and workability.
In addition, the surfactant is also used as an emulsifier for emulsion polymerization used in producing a polymer by emulsion polymerization, and is not only involved in polymerization initiation reaction and growth reaction, but also mechanical stability of the produced emulsion, Also involved in chemical stability, freezing stability, storage stability, etc., emulsion properties such as emulsion particle size, viscosity and foaming properties, water resistance when filmed, weather resistance, adhesion, heat resistance It is known that it has a great influence on film physical properties.
しかしながら、上記のように界面活性剤を乳化剤として使用した場合、乳化重合法により製造した樹脂エマルジョン中に、界面活性剤が遊離した状態で存在するため、エマルジョンの泡立ち、樹脂の耐水性、接着性等に悪影響を及ぼすことが、問題点として指摘されている。 However, when a surfactant is used as an emulsifier as described above, since the surfactant is present in a free state in the resin emulsion produced by the emulsion polymerization method, foaming of the emulsion, water resistance of the resin, adhesiveness It has been pointed out as a problem that it adversely affects
このような問題点を改善すべく、従来の界面活性剤が有する疎水基と親水基とに加え、ラジカル重合性の二重結合を有する反応性界面活性剤が開発されている。このような反応性界面活性剤は、乳化重合の際に生成ポリマー鎖中に共重合するため、遊離した状態の界面活性剤による物性低下を防ぐことが出来る。
例えば、特許文献１には、ジオキソラン環と、共重合性の不飽和基を合わせ持つ化合物からなる新規な反応性乳化剤が開示されており、特許文献２には、疎水基として分岐の脂肪族炭化水素基を有する反応性界面活性剤が開示されている。
In order to improve such problems, reactive surfactants having radical polymerizable double bonds have been developed in addition to the hydrophobic groups and hydrophilic groups of conventional surfactants. Since such a reactive surfactant is copolymerized in the generated polymer chain during emulsion polymerization, it is possible to prevent physical properties from being lowered due to the released surfactant.
For example, Patent Document 1 discloses a novel reactive emulsifier composed of a compound having a dioxolane ring and a copolymerizable unsaturated group, and Patent Document 2 discloses branched aliphatic carbonization as a hydrophobic group. Reactive surfactants having hydrogen groups are disclosed.
一方で、近年は反応性界面活性剤を疎水性物質等の分散に使用することが行われているが、上述のような主に重合乳化剤に使用される反応性界面活性剤は、エマルジョンとの吸着性は充分であるが、疎水性物質の分散に使用する場合は、疎水性物質への吸着性が不充分であるため、好適な分散性を確保できないという問題があった。 On the other hand, in recent years, reactive surfactants have been used to disperse hydrophobic substances and the like. However, reactive surfactants mainly used for polymerization emulsifiers as described above are used with emulsions. Although the adsorptivity is sufficient, when used for dispersion of a hydrophobic substance, there is a problem in that suitable dispersibility cannot be ensured because the adsorptivity to the hydrophobic substance is insufficient.
また、乳化重合用乳化剤だけでなく、樹脂改質剤等にも使用される反応性界面活性剤として、特許文献３に疎水基としてフッ素原子を有する炭化水素基を有する反応性界面活性剤が開示されている。このような反応性界面活性剤は、従来よりも疎水性の強い分子鎖を有するので、疎水性物質への物理的吸着性は多少改善されるものの、化学結合に由来する疎水性物質表面への固定化が不充分であるため、界面活性剤の遊離防止効果についても満足な結果が得られないという問題があった。 Further, as a reactive surfactant used not only for emulsifiers for emulsion polymerization but also for resin modifiers, Patent Document 3 discloses a reactive surfactant having a hydrocarbon group having a fluorine atom as a hydrophobic group. Has been. Such reactive surfactants have molecular chains that are more hydrophobic than in the past, so that the physical adsorption to hydrophobic substances is somewhat improved, but the surface of hydrophobic substances derived from chemical bonds can be improved. Since the immobilization is insufficient, there is a problem that a satisfactory result cannot be obtained with respect to the surfactant release preventing effect.
本発明は、特に疎水性物質の乳化分散に使用する場合に、被分散体からの界面活性剤の遊離を防止しつつ、充分な乳化分散を可能とした反応性界面活性剤及び該反応性界面活性剤を用いた反応性界面活性剤組成物を提供することを目的とする。 The present invention relates to a reactive surfactant capable of sufficient emulsification and dispersion while preventing the release of the surfactant from the dispersion, particularly when used for emulsification and dispersion of hydrophobic substances, and the reactive interface. An object of the present invention is to provide a reactive surfactant composition using an activator.
本発明は、下記式（１）で表される構造を有する反応性界面活性剤及び下記式（２）で表される構造を有する架橋性界面活性剤を含有することを特徴とする反応性界面活性剤組成物である。 The present invention is a reactive surface which is characterized by containing a crosslinkable surface active agent having a structure represented by the reactivity surfactant and the following formula having a structure represented by the following formula (1) (2) Activator composition .
以下、本発明を詳述する。
The present invention is described in detail below.
本発明の反応性界面活性剤は、（メタ）アクリロイル基を有する重合反応性ユニットであるＲ１を有する。上記Ｒ１を有することで、本発明の反応性界面活性剤は、高い重合反応性を示す。
本発明の反応性界面活性剤において、Ｒ１の（メタ）アクリロイル基を有する重合反応性ユニットとしては、例えば、（メタ）アクリロイルメチン、（メタ）アクリロイルアミン、（メタ）アクリロイルエトキシメチン、(メタ)アクリロイルエトキシアミン等が好ましい。
The reactive surfactant of the present invention has R 1 which is a polymerization reactive unit having a (meth) acryloyl group. By having the above R 1, the reactive surfactant of the present invention show a high polymerization reactivity.
In the reactive surfactant of the present invention, examples of the polymerization reactive unit having a (meth) acryloyl group of R 1 include (meth) acryloylmethine, (meth) acryloylamine, (meth) acryloylethoxymethine, (meth ) Acrylylethoxyamine and the like are preferable.
本発明の反応性界面活性剤において、Ｘ１としては、直鎖状の炭化水素を用いることが好ましい。具体的には、直鎖のアルキル基が好ましい。直鎖状とすることで、疎水性物質への吸着性を向上させることができる。分岐鎖状のアルキル基を用いた場合、重合反応性基の立体障害となって反応性が低下するだけでなく、疎水性物質上に配向を持って吸着するのが困難となり、界面活性剤の吸着密度が低下して、分散安定化効果が低下する。 In the reactive surfactant of the present invention, the X 1, it is preferable to use a straight-chain hydrocarbon. Specifically, a linear alkyl group is preferable. Adsorption to a hydrophobic substance can be improved by making it linear. When a branched alkyl group is used, not only is the steric hindrance of the polymerization reactive group, the reactivity is lowered, but also it becomes difficult to adsorb with an orientation on a hydrophobic substance, The adsorption density decreases, and the dispersion stabilization effect decreases.
上記Ｘ１は、炭素数が８〜２０である。上記炭素数が８未満であると、疎水性が低下して、疎水性物質への吸着性に劣るものとなり、上記炭素数が２０を超えると、重合性反応基がアルキル鎖中に埋没してしまい、重合反応性が低下する。好ましくは炭素数１２〜１８であり、より好ましくは炭素数１４〜１８である。 X 1 has 8 to 20 carbon atoms. When the number of carbon atoms is less than 8, the hydrophobicity is lowered and the adsorptivity to the hydrophobic substance is poor. When the number of carbon atoms exceeds 20, the polymerizable reactive group is buried in the alkyl chain. As a result, the polymerization reactivity decreases. Preferably it is C12-18, More preferably, it is C14-18.
上記Ｘ１としては、例えば、オクチル基、ノニル基、デシル基、 ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、オクタデシル基、エイコシル基等が好ましい。なかでも、ヘキサデシル基とオクタデシル基が好ましい。 X 1 is preferably an octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, eicosyl group, and the like. Of these, a hexadecyl group and an octadecyl group are preferable.
本発明の反応性界面活性剤では、Ｙ１として分子量１０００以下の親水性ユニットを用いる。
上記親水性ユニットの分子量の上限は１０００である。分子量１０００を超えると、親水性／疎水性のバランスが悪くなり、界面活性能力が低下する。好ましい上限は６００であり、より好ましい上限は３００である。なお、下限については特に限定されないが、１００が好ましい。
The reactive surfactant of the present invention, a molecular weight of 1,000 or less hydrophilic unit as Y 1.
The upper limit of the molecular weight of the hydrophilic unit is 1000. When the molecular weight exceeds 1000, the hydrophilic / hydrophobic balance is deteriorated, and the surface active ability is lowered. A preferable upper limit is 600, and a more preferable upper limit is 300. In addition, although it does not specifically limit about a minimum, 100 is preferable.
上記Ｙ１としては、ポリエチレングリコール骨格又はポリプロピレングリコール骨格を有するものを用いることが好ましい。
上記ポリエチレングリコール骨格又はポリプロピレングリコール骨格を有することで、分子運動の自由度が高く、溶媒和し易い分子形態をとることができるという利点がある。また、上記親水性ユニットは直鎖状であることが好ましい。直鎖状とすることで、溶媒和がしやすく、極性溶媒中で優れた分散性を発現する。なお一分子あたりの親水基の本数は、１ないし２本であることが好ましい。
この様な特徴はエーテル結合を有する直鎖状分子に共通するものである。
As the Y 1, it is preferable to use those having a polyethylene glycol skeleton or polypropylene glycol skeleton.
By having the polyethylene glycol skeleton or the polypropylene glycol skeleton, there is an advantage that a molecular form having a high degree of freedom of molecular motion and easy to solvate can be obtained. The hydrophilic unit is preferably linear. By making it linear, it is easy to solvate and exhibits excellent dispersibility in a polar solvent. The number of hydrophilic groups per molecule is preferably 1 to 2.
Such characteristics are common to linear molecules having an ether bond.
上記ポリエチレングリコール骨格又はポリプロピレングリコール骨格における重合度が２〜１５であることが好ましい。上記重合度が２未満であると、極性溶媒が溶媒和されにくく不安定となることがあり、１５を超えると親水性の分子量が大きくなり、親水性／疎水性のバランスが悪くなって界面活性能力が低下することがある。より好ましくは４〜１０である。 The degree of polymerization in the polyethylene glycol skeleton or polypropylene glycol skeleton is preferably 2-15. If the degree of polymerization is less than 2, the polar solvent may not be easily solvated and may become unstable. If the degree of polymerization exceeds 15, the hydrophilic molecular weight increases, and the hydrophilic / hydrophobic balance becomes poor, resulting in surface activity. Capability may be reduced. More preferably, it is 4-10.
本発明の反応性界面活性剤は、従来、反応性界面活性剤が用いられてきた用途、即ち、乳化重合用乳化剤、懸濁重合用分散剤等以外にも、疎水性物質の表面改質剤等に使用することができる。特に、カーボンナノチューブや天然黒鉛、グラフェン等の疎水性物質の分散剤として好適に使用することができる。 The reactive surfactant of the present invention is a surface modifier for hydrophobic substances in addition to the applications for which reactive surfactants have been used conventionally, that is, an emulsifier for emulsion polymerization, a dispersant for suspension polymerization, and the like. Can be used for etc. In particular, it can be suitably used as a dispersant for hydrophobic substances such as carbon nanotubes, natural graphite, and graphene.
本発明の反応性界面活性剤を作製する方法としては、例えば、炭素数８〜２０の炭化水素を有するアミン等と、ポリアルキレングリコールのハロゲン化物等を反応させた後、（メタ）アクリロイル基を有する化合物を添加して、（メタ）アクリロイル基を付加する方法等が挙げられる。 As a method for producing the reactive surfactant of the present invention, for example, an amine having a hydrocarbon having 8 to 20 carbon atoms and a halide of polyalkylene glycol are reacted, and then a (meth) acryloyl group is reacted. And a method of adding a (meth) acryloyl group by adding a compound having the above.
上記（メタ）アクリロイル基を有する化合物としては、メタクリロイルクロリド、アクリロイルクロリド、２−クロロエチルアクリレート、２−クロロエチルメタクリレート等が挙げられる。
また、上記（メタ）アクリロイル基を有する化合物に加えて、アリル基又はスチレン基を有する化合物を添加してもよい。
上記アリル基又はスチレン基を有する化合物としては、例えば、臭化アリル、塩化アリル、３−ブルモ−２−メチル−１−プロペン、クロロメチルスチレン等が挙げられる。
Examples of the compound having a (meth) acryloyl group include methacryloyl chloride, acryloyl chloride, 2-chloroethyl acrylate, and 2-chloroethyl methacrylate.
Moreover, in addition to the compound having the (meth) acryloyl group, a compound having an allyl group or a styrene group may be added.
Examples of the compound having an allyl group or styrene group include allyl bromide, allyl chloride, 3-bromo-2-methyl-1-propene, and chloromethylstyrene.
本発明の反応性界面活性剤は、下記式（２）で表される構造を有する架橋性界面活性剤と併用することで、反応性界面活性剤と架橋性界面活性剤とが共重合して、強固な架橋構造が形成され、界面活性剤の遊離を効果的に防止して、更に高い分散安定性を実現することができる。このように、本発明の反応性界面活性剤及び下記式（２）で表される構造を有する架橋性界面活性剤を含有する反応性界面活性剤組成物もまた、本発明の１つである。 When the reactive surfactant of the present invention is used in combination with a crosslinkable surfactant having a structure represented by the following formula (2), the reactive surfactant and the crosslinkable surfactant are copolymerized. A strong cross-linked structure is formed, and the release of the surfactant can be effectively prevented to achieve higher dispersion stability. Thus, the reactive surfactant composition containing the reactive surfactant of the present invention and the crosslinkable surfactant having the structure represented by the following formula (2) is also one aspect of the present invention. .
上記架橋性界面活性剤中のＲ２、Ｒ３、Ｘ２及びＹ２としては、上述したＲ１、Ｘ１及びＹ１と同様のものが例示できる。なお、上記Ｒ１、Ｘ１及びＹ１と、Ｒ２、Ｒ３、Ｘ２及びＹ２とは、同じものであってもよく、異なるものであってもよい。 Examples of R 2 , R 3 , X 2 and Y 2 in the crosslinkable surfactant are the same as those described above for R 1 , X 1 and Y 1 . The above R 1 , X 1 and Y 1 and R 2 , R 3 , X 2 and Y 2 may be the same or different.
本発明の反応性界面活性剤組成物において、上記架橋性界面活性剤の添加量の好ましい下限は、反応性界面活性剤１００モル部に対して０．１モル部、好ましい上限は３０モル部である。架橋性界面活性剤の添加量が０．１モル部未満であると、反応性界面活性剤の遊離防止効果が弱くなり、３０モル部を超えると、被分散体の凝集を招く。より好ましい下限は０．５モル部、より好ましい上限は１０モル部である。 In the reactive surfactant composition of the present invention, the preferable lower limit of the addition amount of the crosslinkable surfactant is 0.1 mol part with respect to 100 mol parts of the reactive surfactant, and the preferable upper limit is 30 mol parts. is there. When the addition amount of the crosslinkable surfactant is less than 0.1 mol part, the effect of preventing the release of the reactive surfactant is weakened, and when it exceeds 30 mol part, aggregation of the dispersion is caused. A more preferred lower limit is 0.5 mole part, and a more preferred upper limit is 10 mole part.
上記架橋性界面活性剤を作製する方法としては、例えば、炭素数８〜２０の炭化水素を有するジアミン等と、ポリアルキレングリコールのハロゲン化物等を反応させた後、（メタ）アクリロイル基を有する化合物を添加して、（メタ）アクリロイル基を付加する方法等が挙げられる。 Examples of the method for producing the crosslinkable surfactant include a compound having a (meth) acryloyl group after reacting a diamine having a hydrocarbon having 8 to 20 carbon atoms with a halide of polyalkylene glycol. And a method of adding a (meth) acryloyl group.
本発明の反応性界面活性剤組成物に、更に、分散媒体、重合開始剤及び被分散体を添加し、反応性界面活性剤を重合することで、被分散体に極めて高い分散安定性を付与することができ、更に、反応性界面活性剤組成物を洗浄した後でも、被分散体の高い分散性を維持することが可能となる。 A dispersion medium, a polymerization initiator and a dispersion are further added to the reactive surfactant composition of the present invention, and the reactive surfactant is polymerized to give extremely high dispersion stability to the dispersion. Further, even after the reactive surfactant composition is washed, it is possible to maintain high dispersibility of the dispersion.
上記分散媒体としては、例えば、水、エタノール、メタノール、トルエン、クロロホルム等が挙げられる。本発明では、特に水およびトルエンを使用する場合に好適に使用することができる。 Examples of the dispersion medium include water, ethanol, methanol, toluene, chloroform, and the like. In the present invention, it can be suitably used particularly when water and toluene are used.
本発明の反応性界面活性剤を分散剤として使用する場合は、重合開始剤を添加することで、反応性界面活性剤を反応させることが可能となる。
上記重合開始剤としては、例えば、アゾビスイソブチロニトリル、２，２′−アゾビス（２−アミノプロパン）ジハイドロクロライド等のアゾ系開始剤、および例えば、ベンゾイルパーオキサイド、ドデシルパーオキサイド等の過酸化物系開始剤が挙げられる。
When using the reactive surfactant of this invention as a dispersing agent, it becomes possible to make a reactive surfactant react by adding a polymerization initiator.
Examples of the polymerization initiator include azo initiators such as azobisisobutyronitrile and 2,2′-azobis (2-aminopropane) dihydrochloride, and examples include benzoyl peroxide and dodecyl peroxide. Peroxide-based initiators may be mentioned.
上記被分散体としては、黒鉛粒子、グラファイト粒子、カーボンナノチューブ、グラフェン、ポリマー粒子、線維、金属微粒子等が挙げられる。
特に、カーボンナノチューブや天然黒鉛、グラフェン等の疎水性物質に使用する場合に、本発明の優れた効果を充分に発揮することができる。
本発明の反応性界面活性剤を疎水性物質の分散剤として使用する場合は、疎水性物質の種類にもよるが、該疎水性物質に対して、好ましくは１０〜１００００重量％使用することが好ましい。
Examples of the dispersion include graphite particles, graphite particles, carbon nanotubes, graphene, polymer particles, fibers, and metal fine particles.
In particular, when used for hydrophobic substances such as carbon nanotubes, natural graphite, and graphene, the excellent effects of the present invention can be sufficiently exhibited.
When the reactive surfactant of the present invention is used as a dispersant for a hydrophobic substance, it is preferably used in an amount of 10 to 10,000% by weight based on the hydrophobic substance, depending on the type of the hydrophobic substance. preferable.
また、本発明の反応性界面活性剤組成物には、重合性のモノマーを添加してもよい。
上記重合性モノマーとしては、特に限定されないが、（メタ）アクリレート、スチレンおよびスチレン誘導体、ビニルエーテル等が挙げられ、これらは単独で用いてもよく、２種以上を併用してもよい。
Further, a polymerizable monomer may be added to the reactive surfactant composition of the present invention.
Although it does not specifically limit as said polymerizable monomer, (meth) acrylate, styrene, a styrene derivative, vinyl ether, etc. are mentioned, These may be used independently and may use 2 or more types together.
さらに、本発明の反応性界面活性剤組成物には、架橋性の多官能性モノマーを添加してもよい。
上記架橋性の多官能性モノマーとしては、特に限定されないが、例えばジ（メタ）アクリレート、トリ（メタ）アクリレート、ジアリル化合物、トリアリル化合物、ジビニル化合物が挙げられ、これらは単独で用いてもよく、２種以上を併用してもよい。
Furthermore, a crosslinkable polyfunctional monomer may be added to the reactive surfactant composition of the present invention.
The crosslinkable polyfunctional monomer is not particularly limited, and examples thereof include di (meth) acrylate, tri (meth) acrylate, diallyl compound, triallyl compound, and divinyl compound, and these may be used alone. Two or more kinds may be used in combination.
本発明の反応性界面活性剤組成物としては、本発明の反応性界面活性剤とカーボン材料を含有し、カーボン材料の表面に本発明の反応性界面活性剤が存在する反応性界面活性剤組成物も含まれる。
このような構成とすることで、疎水性のカーボン材料を親水性の溶媒に容易に分散させることができ、水等の安価な溶液にカーボン材料が分散した分散液を得ることが出来る。
As the reactive surfactant composition of the present invention, the reactive surfactant composition of the present invention contains the reactive surfactant of the present invention and a carbon material, and the reactive surfactant of the present invention is present on the surface of the carbon material. Things are also included.
With such a configuration, the hydrophobic carbon material can be easily dispersed in a hydrophilic solvent, and a dispersion liquid in which the carbon material is dispersed in an inexpensive solution such as water can be obtained.
上記カーボン材料としては、特に限定されないが黒鉛粒子、カーボンナノチューブ、グラフェン等が挙げられる。 Examples of the carbon material include, but are not limited to, graphite particles, carbon nanotubes, graphene, and the like.
本発明の反応性界面活性剤によれば、特に疎水性物質の乳化分散に使用する場合に、被分散体からの界面活性剤の遊離を防止しつつ、充分な乳化分散を可能となる。特に、本発明の反応性界面活性剤によれば、反応後に洗浄した場合でも、優れた分散安定性を維持することができる。 According to the reactive surfactant of the present invention, particularly when used for emulsifying and dispersing hydrophobic substances, sufficient emulsifying and dispersing can be achieved while preventing the release of the surfactant from the dispersion. In particular, the reactive surfactant of the present invention can maintain excellent dispersion stability even when washed after the reaction.
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（合成例１）
Octadecylamine（１．０ｍｍｏｌ）とtriethyleneglycol2-bromoethylmethylether（１．１ｍｍｏｌ）とをN,N-dimethylformamide（ＤＭＦ、２０ｍｌ）に溶解させた後、potassiumcarbonate（１．２ｍｍｏｌ）を加え、１１０℃、窒素雰囲気下の条件で三つ口フラスコを用いて２４時間反応させた。反応終了後、固体成分を熱時ろ過し、溶媒を減圧留去した。残留成分をethylacetate（２０ｍｌ）に溶かし、サンプル瓶中で水と接触させ２層が混合しないように穏やかに撹拌した。水相は約３０分毎に交換し、３回交換を行った。洗浄後のethylacetate層を回収し、magnesiumsulfateを加え、冷蔵庫で一晩静置した。静置後、magnesiumsulfateをろ過で除き、溶媒を減圧留去し、改めてethylacetate （２０ｍｌ）に溶かしpotassiumcarbonate（１．２ｍｍｏｌ）を加えた後、少量のethylacetateに溶かしたmethacryloyl chloride（１．３ｍｍｏｌ）を平衡滴下漏斗で滴下し、滴下終了後２時間反応させた。
反応終了後、固体成分をろ過し、溶媒を減圧留去した。残留成分をethylacetate（２０ｍｌ）に溶かし、サンプル瓶中で水と接触させ２層が混合しないように穏やかに撹拌した。水相は約３０分毎に交換し、３回交換を行った。洗浄後のethylacetate層を回収し、magnesiumsulfateを加え、冷蔵庫で一晩静置した。静置後、magnesiumsulfateをろ過で除き、溶媒を減圧留去し、反応性界面活性剤（Ａ）を得た。
なお、得られた反応性界面活性剤（Ａ）について、ＮＭＲ、ＭＡＬＤＩ−ＴＯＦ−ＭＳを用いて確認したところ、式（３）に示す構造を有することが確認できた。
(Synthesis Example 1)
Octadecylamine (1.0 mmol) and triethyleneglycol 2-bromoethylmethylether (1.1 mmol) are dissolved in N, N-dimethylformamide (DMF, 20 ml), potassium carbonate (1.2 mmol) is added, and the conditions under a nitrogen atmosphere at 110 ° C. And reacted for 24 hours using a three-necked flask. After completion of the reaction, the solid component was filtered while hot, and the solvent was distilled off under reduced pressure. The remaining components were dissolved in ethylacetate (20 ml) and contacted with water in a sample bottle and gently stirred so that the two layers did not mix. The aqueous phase was changed about every 30 minutes and changed three times. The ethylacetate layer after washing was collected, magnesiumsulfate was added, and the mixture was allowed to stand overnight in a refrigerator. After standing, the magnesiumsulfate is removed by filtration, the solvent is distilled off under reduced pressure, dissolved again in ethylacetate (20 ml), potassium carbonate (1.2 mmol) is added, and then a small amount of ethylacetate dissolved in methacryloyl chloride (1.3 mmol) is equilibrated. The solution was added dropwise using a dropping funnel and reacted for 2 hours after completion of the dropping.
After completion of the reaction, the solid component was filtered and the solvent was distilled off under reduced pressure. The remaining components were dissolved in ethylacetate (20 ml) and contacted with water in a sample bottle and gently stirred so that the two layers did not mix. The aqueous phase was changed about every 30 minutes and changed three times. The ethylacetate layer after washing was collected, magnesiumsulfate was added, and the mixture was allowed to stand overnight in a refrigerator. After standing, the magnesiumsulfate was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a reactive surfactant (A).
In addition, about the obtained reactive surfactant (A), when it confirmed using NMR and MALDI-TOF-MS, it has confirmed having the structure shown to Formula (3).
（合成例２）
1,12-Diaminododecane（１．０ｍｍｏｌ）とtriethyleneglycol2-bromoethylmethylether
（２．２ｍｍｏｌ）をN,N-dimethylformamide（ＤＭＦ、２０ｍｌ）に溶かし、potassiumcarbonate（３．０ｍｍｏｌ）を加え、１１０℃、窒素雰囲気下の条件で三つ口フラスコを用いて２４時間反応させた。反応終了後、固体成分を熱時ろ過し、溶媒を減圧留去した。残留成分をethylacetate（２０ｍｌ）に溶かし、サンプル瓶中で水と接触させ２層が混合しないように穏やかに撹拌した。水相は約３０分毎に交換し、３回交換を行った。洗浄後のethylacetate層を回収し、magnesiumsulfateを加え、冷蔵庫で一晩静置した。静置後、magnesiumsulfateをろ過で除き、溶媒を減圧留去し、残留成分をdichloromethane（Ｄ
ＣＭ，２０ｍｌ）に溶かし、potassiumcarbonate（３．０ｍｍｏｌ）を加えた後、少量のＤＣＭに溶かしたmethacryloyl chloride（２．２ｍｍｏｌ）を平衡滴下漏斗で滴下した
。滴下終了後２時間反応させた。反応終了後、固体成分をろ過し、溶媒を減圧留去した。残留成分をethylacetate（２０ｍｌ）に溶かし、サンプル瓶中で水と接触させ２層が混合しないように穏やかに撹拌した。水相は約３０分毎に交換し、３回交換を行った。洗浄後のethylacetate層を回収し、magnesiumsulfateを加え、冷蔵庫で一晩静置した。静置後、magnesiumsulfateをろ過で除き、溶媒を減圧留去し、架橋性界面活性剤（Ａ）を得た。
なお、得られた架橋性界面活性剤（Ａ）について、ＮＭＲ、ＭＡＬＤＩ−ＴＯＦ−ＭＳを用いて確認したところ、式（４）に示す構造を有することが確認できた。
(Synthesis Example 2)
1,12-Diaminododecane (1.0 mmol) and triethyleneglycol 2-bromoethylmethylether
(2.2 mmol) was dissolved in N, N-dimethylformamide (DMF, 20 ml), potassium carbonate (3.0 mmol) was added, and the reaction was carried out for 24 hours using a three-necked flask at 110 ° C. under a nitrogen atmosphere. After completion of the reaction, the solid component was filtered while hot, and the solvent was distilled off under reduced pressure. The remaining components were dissolved in ethylacetate (20 ml) and contacted with water in a sample bottle and gently stirred so that the two layers did not mix. The aqueous phase was changed about every 30 minutes and changed three times. The ethylacetate layer after washing was collected, magnesiumsulfate was added, and the mixture was allowed to stand overnight in a refrigerator. After standing, the magnesiumsulfate is removed by filtration, the solvent is distilled off under reduced pressure, and the residual component is dichloromethane (D
CM, 20 ml), potassium carbonate (3.0 mmol) was added, and then methacryloyl chloride (2.2 mmol) dissolved in a small amount of DCM was added dropwise with an equilibrium dropping funnel. It was made to react for 2 hours after completion | finish of dripping. After completion of the reaction, the solid component was filtered and the solvent was distilled off under reduced pressure. The remaining components were dissolved in ethylacetate (20 ml) and contacted with water in a sample bottle and gently stirred so that the two layers did not mix. The aqueous phase was changed about every 30 minutes and changed three times. The ethylacetate layer after washing was collected, magnesiumsulfate was added, and the mixture was allowed to stand overnight in a refrigerator. After standing, the magnesiumsulfate was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a crosslinkable surfactant (A).
In addition, about the obtained crosslinkable surfactant (A), when it confirmed using NMR and MALDI-TOF-MS, it has confirmed having the structure shown to Formula (4).
（合成例３）
Octadecylamine（１．０ｍｍｏｌ）に代えて、Dodecylamine（１．０ｍｍｏｌ）を用いた以外は合成例１と同様にして、反応性界面活性剤（Ｆ）を得た。
なお、得られた反応性界面活性剤（Ｆ）は、式（１）に示す構造を有するものであり、Ｘ１はドデシル基であった。
(Synthesis Example 3)
A reactive surfactant (F) was obtained in the same manner as in Synthesis Example 1, except that Dodecylamine (1.0 mmol) was used instead of Octadecylamine (1.0 mmol).
Incidentally, the obtained reactive surfactant (F) are those having the structure shown in formula (1), X 1 was dodecyl.
（参考例１）
（カーボンナノチューブ分散液の調製）
合成例１で得られた反応性界面活性剤（Ａ）１００ｍｇ、カーボンナノチューブ（アルドリッチ社製）１ｍｇ、重合開始剤として２，２′−アゾビス（２−アミノプロパン）ジハイドロクロライド（Ｖ−５０、和光純薬工業社製）１ｍｇを、イオン交換水１ｍＬに添加し、超音波によってカーボンナノチューブを水溶液中に分散させることで、カーボンナノチューブ分散液を作製した。
( Reference Example 1)
(Preparation of carbon nanotube dispersion)
100 mg of the reactive surfactant (A) obtained in Synthesis Example 1, 1 mg of carbon nanotubes (manufactured by Aldrich), 2,2′-azobis (2-aminopropane) dihydrochloride (V-50, as a polymerization initiator) 1 mg of Wako Pure Chemical Industries, Ltd.) was added to 1 mL of ion-exchanged water, and the carbon nanotubes were dispersed in an aqueous solution by ultrasonic waves to prepare a carbon nanotube dispersion.
（参考例２）
参考例１において、Ｖ−５０に代えてアゾビスイソブチロニトリル、イオン交換水に代えてトルエンを使用した以外は参考例１と同様にしてカーボンナノチューブ分散液を作製した。
( Reference Example 2)
A carbon nanotube dispersion was prepared in the same manner as in Reference Example 1 except that azobisisobutyronitrile was used instead of V-50 and toluene was used instead of ion-exchanged water in Reference Example 1.
（実施例３）
（カーボンナノチューブ分散液の調製）
合成例１で得られた反応性界面活性剤（Ａ）１００ｍｇ、合成例２で得られた架橋性界面活性剤（Ａ）１ｍｇ、カーボンナノチューブ（アルドリッチ社製）１ｍｇ、Ｖ−５０（重合開始剤）１ｍｇをイオン交換水１ｍＬに添加し、超音波によってカーボンナノチューブを水溶液中に分散させることで、カーボンナノチューブ分散液を作製した。なお、反応性界面活性剤（Ａ）１００モル部に対する架橋性界面活性剤（Ａ）の添加量は１モル部であった。
(Example 3)
(Preparation of carbon nanotube dispersion)
100 mg of the reactive surfactant (A) obtained in Synthesis Example 1, 1 mg of the crosslinkable surfactant (A) obtained in Synthesis Example 2, 1 mg of carbon nanotubes (manufactured by Aldrich), V-50 (polymerization initiator) ) 1 mg was added to 1 mL of ion-exchanged water, and the carbon nanotubes were dispersed in an aqueous solution by ultrasonic waves to prepare a carbon nanotube dispersion. In addition, the addition amount of the crosslinkable surfactant (A) with respect to 100 mol parts of the reactive surfactant (A) was 1 mol part.
（実施例４）
実施例３において、Ｖ−５０に代えてアゾビスイソブチロニトリル、イオン交換水に代えてトルエンを使用した以外は実施例３と同様にしてカーボンナノチューブ分散液を作製した。
Example 4
In Example 3, a carbon nanotube dispersion was prepared in the same manner as in Example 3 except that azobisisobutyronitrile was used instead of V-50, and toluene was used instead of ion-exchanged water.
（参考例５）
（天然黒鉛分散液の調製）
参考例１において、カーボンナノチューブ１ｍｇに代えて天然黒鉛粉末（ＳＥＣカーボン社製 ＳＮＯ−１５）１０ｍｇを使用した以外は参考例１と同様にして天然黒鉛分散液を作製した。
( Reference Example 5)
(Preparation of natural graphite dispersion)
A natural graphite dispersion was prepared in the same manner as in Reference Example 1 except that 10 mg of natural graphite powder (SNO-15 manufactured by SEC Carbon Co.) was used instead of 1 mg of carbon nanotubes in Reference Example 1.
（実施例６）
実施例３において、カーボンナノチューブ１ｍｇに代えて天然黒鉛粉末（ＳＥＣカーボン社製 ＳＮＯ−１５）１０ｍｇを使用した以外は実施例３と同様にして天然黒鉛分散液を作製した。
(Example 6)
A natural graphite dispersion was prepared in the same manner as in Example 3, except that 10 mg of natural graphite powder (SNO-15 manufactured by SEC Carbon Co.) was used instead of 1 mg of carbon nanotubes.
（参考例７）
参考例５において、合成例１で得られた反応性界面活性剤（Ａ）１００ｍｇに代えて、合成例３で得られた反応性界面活性剤（Ｆ）１００ｍｇを使用した以外は参考例５と同様にして天然黒鉛分散液を作製した。
( Reference Example 7)
Reference Example 5, instead of the reactive surfactant (A) 100 mg obtained in Synthesis Example 1, except for using a reactive surfactant obtained in Synthesis Example 3 (F) 100 mg is to Reference Example 5 A natural graphite dispersion was prepared in the same manner.
（比較例１〜４）
参考例１において、合成例１で得られた反応性界面活性剤（Ａ）１００ｍｇに代えて、下記に示す反応性界面活性剤（Ｂ）〜（Ｅ）１００ｍｇを使用した以外は参考例１と同様にしてカーボンナノチューブ分散液を作製した。
反応性界面活性剤（Ｂ）：ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸アンモニウム（アクアロンＨＳ−１０、第一工業製薬社製）
反応性界面活性剤（Ｃ）：ポリオキシエチレン−１−（アリルオキシメチル）アルキルエーテル硫酸アンモニウム（アクアロンＫＨ−１０、第一工業製薬社製）
反応性界面活性剤（Ｄ）：ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸アンモニウム（アクアロンＢＣ−１０、第一工業製薬社製）
反応性界面活性剤（Ｅ）：ポリオキシエチレンノニルプロペニルフェニルエーテル（アクアロンＲＮ−５０、第一工業製薬社製）
(Comparative Examples 1-4)
Reference Example 1 in place of the reactive surfactant obtained in Synthesis Example 1 (A) 100 mg, except for using the reactive surfactant (B) ~ (E) 100mg shown below in Reference Example 1 Similarly, a carbon nanotube dispersion was prepared.
Reactive surfactant (B): Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Reactive surfactant (C): Polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate (Aqualon KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Reactive surfactant (D): Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (Aqualon BC-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Reactive surfactant (E): Polyoxyethylene nonylpropenyl phenyl ether (Aqualon RN-50, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
（比較例５〜８）
比較例１〜４において、Ｖ−５０に代えてアゾビスイソブチロニトリル、イオン交換水に代えてトルエンを使用した以外は比較例１〜４と同様にしてカーボンナノチューブ分散液を作製した。
(Comparative Examples 5 to 8)
In Comparative Examples 1 to 4, carbon nanotube dispersions were prepared in the same manner as in Comparative Examples 1 to 4, except that azobisisobutyronitrile was used instead of V-50, and toluene was used instead of ion-exchanged water.
（評価方法）
上記で得られた反応性界面活性剤の性能を以下の方法で評価した。結果を表１に示した。
(Evaluation method)
The performance of the reactive surfactant obtained above was evaluated by the following method. The results are shown in Table 1.
（１）重合前の分散安定性評価
実施例、参考例及び比較例で得られたカーボンナノチューブ分散液あるいは天然黒鉛分散液について、３０分間静置した後、固形の沈降堆積物が目視で確認できなかった場合を「○（分散）」、固形の沈降堆積物は確認できないが、やや濁りが見られた場合を「△」、固形の沈降堆積物が確認できた場合を「×（沈殿）」として評価した。
(1) Evaluation of dispersion stability before polymerization The carbon nanotube dispersions or natural graphite dispersions obtained in Examples , Reference Examples and Comparative Examples were allowed to stand for 30 minutes, and solid sedimentation deposits could be visually confirmed. “○ (dispersion)” when there was not, solid sedimentation deposits could not be confirmed, “△” when some turbidity was observed, “× (precipitation)” when solid sedimentation deposits could be confirmed As evaluated.
（２）重合後の分散安定性評価
実施例、参考例及び比較例で得られたカーボンナノチューブ分散液あるいは天然黒鉛分散液を、溶媒がイオン交換水である場合は５０℃（溶媒がトルエンである場合は８０℃）で１２０分間加熱した後、３０分間静置し、固形の沈降堆積物が目視で確認できなかった場合を「○（分散）」、固形の沈降堆積物は確認できないが、やや濁りが見られた場合を「△」、固形の沈降堆積物が確認できた場合を「×（沈殿）」として評価した。
(2) Evaluation of dispersion stability after polymerization The carbon nanotube dispersion or the natural graphite dispersion obtained in Examples , Reference Examples and Comparative Examples is 50 ° C. when the solvent is ion-exchanged water (the solvent is toluene). In this case, after heating for 120 minutes at 80 ° C., the mixture was allowed to stand for 30 minutes, and solid sedimentation deposits could not be visually confirmed as “◯ (dispersion)”. The case where turbidity was observed was evaluated as “Δ”, and the case where a solid sediment was confirmed was evaluated as “× (precipitation)”.
（３）洗浄後の分散安定性評価
「（２）重合後の分散安定性評価」を行った後のカーボンナノチューブ分散液あるいは天然黒鉛分散液３０ｍｌを遠心分離機にて２００００回転３０分間遠心沈降させた。上層の溶媒（イオン交換水またはトルエン）を除去した後、沈降物に再び分散に用いたのと同じ溶媒（イオン交換水またはトルエン）３０ｍｌを加え、超音波分散を行った。上記の洗浄操作を３回繰り返した後、３０分間静置し、様子を目視で観察してカーボンナノチューブあるいは天然黒鉛分散液の分散性を確認した。固形の沈降堆積物が目視で確認できなかった場合を「○（分散）」、固形の沈降堆積物は確認できないが、やや濁りが見られた場合を「△」、固形の沈降堆積物が確認できた場合を「×（沈殿）」として評価した。
(3) Dispersion stability evaluation after washing “(2) Dispersion stability evaluation after polymerization” 30 ml of the carbon nanotube dispersion or natural graphite dispersion was centrifuged at 20,000 rpm for 30 minutes in a centrifuge. It was. After removing the upper layer solvent (ion-exchanged water or toluene), 30 ml of the same solvent (ion-exchanged water or toluene) used for dispersion was added again to the sediment, and ultrasonic dispersion was performed. The above washing operation was repeated three times, and then allowed to stand for 30 minutes, and the state was visually observed to confirm the dispersibility of the carbon nanotube or the natural graphite dispersion. “○ (dispersion)” when solid sedimentation deposits could not be confirmed visually, solid sedimentation sediments could not be confirmed, but “△” when slight turbidity was observed, solid sedimentation deposits confirmed The case where it was made was evaluated as “× (precipitation)”.
本発明によれば、特に疎水性物質の乳化分散に使用する場合に、被分散体からの界面活性剤の遊離を防止しつつ、充分な乳化分散を可能とした反応性界面活性剤及び該反応性界面活性剤を用いた反応性界面活性剤組成物を提供することができる。 According to the present invention, particularly when used for emulsifying and dispersing hydrophobic substances, the reactive surfactant capable of sufficiently emulsifying and dispersing while preventing the release of the surfactant from the dispersion, and the reaction A reactive surfactant composition using a reactive surfactant can be provided.
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