The detergency of oily soil was studied from the viewpoint of control of textile/oil/water interface. In this review, the wetting of textile assemblies is chiefly discussed to study the sur-face free energies. It was made clear that such information can be obtained by (1) the exact consideration of geometrical structure of textile surface, and/or (2) the comparison of the results of other surface analyses, such as FT-IR, ESCA and so on, of the fabrics with those of flat films of same substrates whose surface free energies are known. The role of the control of textile surface on the removal, using for an example the soil-release finishing, is also discussed in terms of work of adhesion.

抄録全体を表示

TMS化をしないスフィンゴ塩基のトレオ体とエリトロ体を高感度で順相HPLC-UVで定量する方法を確立するため, ラベル化 (芳香化) 剤として各種の置換基を持つN-スクシンイミジルベンゾエート (2) を用い, 合成したCn-ジヒドロスフィンゴシン (1) を標準サンプルとして検討した。 (2) による (1) のラベル化はアセトニトリル中で両者を還流することにより容易に起こり, 254nmに吸収を持つN-アリールカルボニル化合物 (3) が定量的に得られた。 (1) のエリトロ体とトレオ体は (3) の形で順相HPLCで分離でき, そのクロマトグラムから求めた (1) のエリトロ体の含量は (2) の置換基に無関係に一定であるとともに, (3) のO, O-di-TMS誘導体を用いたGLC分析の結果と良好な一致を示した。

抄録全体を表示

本研究は多峰型細孔分布を有する4種の球状合成炭素質吸着剤上での, pHで分画したフミン質フラクションの吸着特性に関するものである。純水及び0.1N水酸化ナトリウム溶液に溶解させた両フミン質フラクションの分子量は, ゲル濾過クロマトグラフィーにより約100から100000 (ポリエチレングリコール又はポリエチレンオキシドとして) を越える範囲で, 見掛け上, それぞれ3成分及び2成分に分画された。この両フミン質フラクションは, 直径50A以下に多量の細孔を持つ吸着剤でよく吸着された。純水及び0.1N水酸化ナトリウム溶液に溶解した両フミン質フラクションの平均分子径は, 光散乱法によればそれぞれ17A及び23Aであった。フミン質フラクションの吸着速度に関しては, フラクション及びそのフラクション中のフミン質成分の分子径が小さくなるにつれ速くなった。これらの結果から水に溶存するフミン質の完全除去には, フミン質の粒径測定と, それに適合した細孔を充分に持つ炭素質吸着剤の選択が重要であることが示唆された。

抄録全体を表示

Ru/SiO2 catalysts were prepared by impregnating RuCl3·nH2O into silica in a series of solvents which can coordinate to metal ions and activating in hydrogen. The effects of the im-pregnation solvents on the Ru/SiO2 catalyzed hydrogenation of benzene were investigated. In the catalysts activated in hydrogen without calcination, cyclohexene yields were in the range of 9 to 25 depending on the complexing ability of the preparation solvents. When the impregnation solvents had strong coordination ability, the catalysts showed low cyclohexene yields. But when the impregnation solvents had weak coordination ability, the catalysts showed high cyclohexene yields. For instance, 2-aminoethanol and ethanol gave the catalysts showing the highest and lowest cyclohexene yields respectively. When the catalysts were activated in hydrogen after cal-cination, all the catalysts showed almost the same cyclohexene yields in spite of the different kinds of impregnation solvents. The visible spectra of the catalyst preparation solutions and thermogravimetric analyses of non-calcined catalysts indicated that differences between the catalysts with and without calcination is due to inclusion of impregnation solvents in non-calcinated catalysts after activation.

抄録全体を表示

The surface adsorbability of a cationic surfactant on nylon 6 fibers grafted with acrylic and methacrylic acids was studied by measuring the ζ-potential of the fibers in an aqueous solution of the surfactant, N-dodecylpyridinium bromide (DPB). The amount of adsorbed DPB per unit area of the fibers was calculated from the ζ-potential value. With increase in DPB concentration, the ζ-potentials of the ungrafted and the grafted fibers changed from negative to positive in sign and the amount of DPB adsorbed increased. Thus possibly, electrostatic and van der Waals forces between the fibers and cationic surfactant may contribute to surface adsorbability. The amount of DPB adsorbed decreased with increase in the degree of grafting.
The free energy of adsorption (ΔG) of DPB on the fibers was calculated from the equation of Ottewill-Watanabe. With increase in the degree of grafting, the negative value of ΔG decreased. The positive entropy of adsorption of the ungrafted and the grafted fibers indicates entropic interactions (the formation of hydrophobic bonds) to possibly be important as the driving force for the adsorption of DPB on the surfaces of the fibers.
Based on the above findings, the surface adsorbability of the cationic surfactant on the grafted fibers is concluded to be less than that on ungrafted fibers since the water-soluble polymer layer was formed at fiber surfaces by grafted polymer chains.

抄録全体を表示

The authors previously reported that polyunsaturated fatty acids having 1, 4-diene structure can be easily conjugated at ordinary temperature using iodine as a photosensitizes.
This paper describes the optimum conditions for the iodine-sensitized conjugation of methyl linoleate under irradiation with a 100W high-pressure mercury lamp and the mechanism involved.
A nonpolar solvent such as petroleum ether was used in this reaction. The optimum conditions of the reaction were as follows : approximately 0.1% of the amount of iodine added; 10% of the concentration of linoleate; room temperature; and irradiation for 1.5h with a mercury lamp.Under these conditions, methyl linoleate was converted to conjugated dienoates in yields of approximately 80% along with small quantities of methyl trans-octadecenoates and polymers. No positional transfer selectivity of double bonds could be detected at all. The conjugated pro-ducts were present in equal amounts as a mixture of methyl 9, 11- and 10, 12-octadecadienoates (the ratio of the cis, trans and trans, trans forms was 3 : 7).
It is considered that iodine atoms react only with the 1, 4-diene system in this iodine-sensitized conjugation to first form a bridged iodoalkyl radical intermediate which is subsequently converted mainly into cis, trans conjugated forms accompanied by a shift of hydrogen and finally the geometrical isomerization equilibrium mentioned above is attained.

抄録全体を表示

In the previous paper, we reported the optimum conditions for the iodine-sensitized conjugation of methyl linoleate and its reaction mechanism.
This paper discusses isomerization arising from irradiation with a 100W high-pressure mercury lamp using methyl linolenate with a 1, 4, 7-triene structure. Conjugated diene-trienoates and small amounts of conjugated trienoates are formed in this reaction. Slightly milder conditions than in methyl linoleate are suitable for the formation of conjugated diene-trienoates. The reaction conducted at room temperature using a sample with a concentration of 10 to 20% adding approximately 0.1% of iodine to a nonpolar solvent such as petroleum ether by irradiation for 46h is considered optimum. To obtain conjugated trienoates mainly, however, milder conditions such as no more than 0.03% iodine should be used. Under such conditions, the amounts of conjugated compounds were as much as about 70% (conjugated diene-trienoates 5562%; conjugated trienoates 815%) of the reaction products.
This sensitized isomerization proceeds in the same way as indicated in the previous report and double bonds shift only in the direction of the conjugation.

抄録全体を表示

Polyunsaturated fatty acids and their derivatives having the 1, 4-diene structure are conjugated easily at ordinary temperature in the presence of iodine by photoirradiation.
The side reaction was investigated in detail in the present study. Addition of excess iodine to a mixture of monoenes and polyenes caused formation of petroleum ether-insoluble polymers from polyene compounds while monoene compounds remained unchanged under these conditions. Thus, polyene compounds can be selectively removed from a mixture of monoenes and polyenes by the iodine-sensitized method.
An example of the purification of monoene compounds is presented below. Methyl esters of tsubaki fatty acids (C16 9.8%; C16 : 1 trace; C18 2.8%; C18 : 1 82.9%; C18 : 2 4.1%; C18 : 3 0.4%) were treated by the urea adducts method. The iodine-sensitized method was carried out on the mother liquor followed by rectification and methyl oleate with a purity of 99.6% was obtained in yields of 66%.
Since this method can be also carried out in the sunlight, it is suited for conducting large scale reactions.

抄録全体を表示

昭和63年6月に工業技術院からの依頼により, 日本石鹸洗剤工業会においてJIS合成洗剤試験方法ならびに合成洗剤の生分解度試験方法の改正原案が作成され, 平成元年3月に答申が行われた。工業技術院では, 過日, 化学製品部会においてこれら2件について議決した。予定では明春に刊行される手筈となっている。
これに関連して, 従来のJISの中で日本石鹸洗剤工業会認定, あるいは日本油化学協会認定として取り扱われてきた数種の試薬について, 新しいJISでは「日本油化学協会が制定した品質規格 (試験方法を含む) がある」との表現によって処置したいとの意向が, 当局より日本石鹸洗剤工業会に伝えられた。これに該当する物質はカルボキシメチルセルロースナトリウム, 直鎖アルキルベンゼンスルホン酸ナトリウム, ドデセン-1 LAS (直鎖ドデシルベンゼンスルホン酸ナトリウム), n-ドデシル=ポリ (オキシエチレン) =エーテル (エチレンオキシドの付加モル数7mol) の4種である。
日本油化学協会は日本石鹸洗剤工業会の委嘱を受けて, 上記に関する検討を合成洗剤部会で実施することを昭和63年9月の理事会で決定した。これを受けて合成洗剤部会の中に合成洗剤JIS関連物質試験方法制定専門委員会が組織された。同委員会は平成元年1月より9月まで4回開催され, 慎重に討議を重ね, この度4種の試験方法を作成したので, とりまとめてここに報告する。

抄録全体を表示