巻号一覧
23 巻, 2 号
選択された号の論文の7件中1～7を表示しています
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久世 栄一, 古島 昭雄1967 年 23 巻 2 号 p. 47-50
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーThe kinetic frictions of lubricated surfaces of solids were measured and the differences in the friction between low energy surfaces like fibres and high energy surfaces like metals were investigated. Straight-chain fatty acids and these copper soaps were employed as lubricants.
If new lubricant is not formed on the lubricated surface by the reaction of the lubricant with the surface of the solid, the chemical property of the surface has the following influences on the friction:
1. When a good lubricant that has long enough chain length is employed, the property of the surface has no influence.
2. When a poor lubricant that has short chain length is employed, the lubrication of fibres is more difficult than that of metals. And the friction of poorly lubricated fibres is higher than that of metals.抄録全体を表示PDF形式でダウンロード (304K) -
第1報 ポリエチレン1, 2-ジフェノキシエタン-p, p′-ジカルボキシレート今村 力造, 清造 剛, 山本 吉威, 三軒 齊, 堀尾 正雄1967 年 23 巻 2 号 p. 51-57
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーPolyethylene 1, 2-diphenoxyethane-p, p′-dicarboxylate (I) is crystalline and melt-spinnable. The purpose of the present work is to determine in detail the physical properties of (I) and to use the results for the discussion of the properties of the polyether-ester homologs having side substituents in the benzene ring, which will be reported in later papers.
The crystallization rate of (I) was estimated from the curves obtained by plotting the specific gravity change at several fixed temperatures against treating times, and it was found that a characteristic feature of (I) is its ease of crystallization. The glass transition-, the cold crystallization-, and the melting temperatures, were estimated by DTA as 71°C, 85°C and 240°C, respectively. The infrared spectrum of (I) was compared with that of polyethylene terephthalate and the assignments of the bands observed were made. It was shown that the drawn and annealed fibers have a high range of tenacity and high initial Young's moduli. In addition, the results obtained are discussed collectively with respect to the molecular structure.抄録全体を表示PDF形式でダウンロード (1112K) -
第2報 ポリエチレン1, 2-ジ(o-メチルフェノキシ)エタン-p, p′-ジカルボキシレート今村 力造, 清造 剛, 山本 吉威, 三軒 齊, 堀尾 正雄1967 年 23 巻 2 号 p. 58-63
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリー1, 2-di (o-methylphenoxy) ethane-p, p′-dicarboxylic acid (A) was derived from o-cresol by our own procedure. The polyether-ester (I) having the following chemical formula was then prepared by the polycondensation of the dimethyl-ester of (A) with ethylene glycol.
The effects of the CH3-group in the benzene ring on the fiber-forming propertes of (I) were studied in comparisen with those of the H-atom of polyethylene 1, 2-diphenoxyethane-p, p′-dicarboxylate (II), as well as those of the CH3O-group of polyethylene 1, 2-di (o-methoxyphenoxy) ethane-p, p′-dicarboxylate (III) reported in the previous paper.
The crystallization rate was measured and it was found that the ease of crystallization is in the
order of H->CH3-_??_CH3O- with respect to the side groups. By differential thermal analysis, it was shown that the glass transition temperature, the melting point and the cold crystallization temperature are in the following order: H-=CH3-<CH3O-, H-=CH3->CH3O-and H-<CH3-, respctively. The fiber periods of (I), (II) and (III) calculated from X-ray fiber diagrams were slightly less than the length of a repeating unit required for fully extended planar zig-zag chains. In addition, the mechanical properties of the drawn and annealed fibers were investigated, and it was shown that the Young's modulus of (I) is as high as that of (II).
In conclusion, it may be said that the effect of the methyl side group in the ortho-position for the ethylene ether linkage is not very large and therefore (I) has the good fiber-forming properties similar to those of (II).抄録全体を表示PDF形式でダウンロード (984K) -
小西 孝, 近藤 宗夫, 黒川 昌孝1967 年 23 巻 2 号 p. 64-69
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーWhen aqueous solution of silk fibroin are acted on by chymotrypsin, a precipitate (Fcp) is formed. Its molecular weight is estimated at about 3, 000 by means of the titration of terminal amino acids. From the result of paperchromatography, it is ascertained that the Fcp is composed of the four amino acid residues of glycine, alanine, serine and tyrosine.
When the Fcp is dissolved in cupri-ethylenediamine and dialyzed, a white precipitate (Fcp 1×) of about 80 weight percent of the original Fcp is obtained again.
The X-ray powder diffraction patterns of the Fcp show that its structure is highly crystalline and resembles closely to the β-structure of fibroin proposed by ‘Shimizu’. The electron micrograph of the Fcp shows that small rod-shaped particles aggregate ramdomly. The X-ray diffraction patterns of the Fcp 1× resemble in α-structure of fibroin proposed by ‘Shimizu’ and show higher crystallinity than the Fcp. The electron micrograph of the Fcp 1× shows the spherulitic aggregates formed by the fibrillar single crystal.
From the reciprocal lattice patterns on xy-plane estimated from the selected area diffraction patterns, it may be expected that α-structure of fibroin is orthorhombic and has the dimensions, 7.20A, 4.49A and C-axis (chain axis) perpendicular to xy-plane. Selected area micrograph shows that the planes correspond to plane distance 7.20A and 4.49A are oriented parallel to and perpendicular to the fibrillar axis respectively.抄録全体を表示PDF形式でダウンロード (3938K) -
第3報 各種化学処理羊毛ヘのメチルメタアクリレートのグラフト共重合新井 幸三, 根岸 道治, 市川 林次郎, 岡田 定行1967 年 23 巻 2 号 p. 70-78
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーIn order to clarify the grafting mechanisms in aqueous lithium bromide-potassium persulfate redox system and potassium persulfate system. Methyl-methacrylate (MMA) grafting was performed onto modified wool and silk fibroin fibers at 30°C and 40°C. In the LiBr-K2S2O8 system, MMA grafton for wool is diminished by pre-treatment with aqueous bromine, peracetic acid, acetic anhydride, diazomethane, 2:4-dinitrofluorobenzene and nitric acid. On the other hand, in the K2S2O8 system, the graft-on is diminished by acetic anhydride, 2:4-dinitrofluorobenzene and nitric acid, but not changed by diazomethane. In the LiBr-K2S2O8 system, MMA graft-on for silk is diminished by the treatment with aqueous bromine, diazomethane, acetic anhydride and nitric acid. In the K2S2O8 system, however, the graft-on is not changed by all the treatments except nitric acid leading to decrease. The grafting onto the wool fibers treated with absolute alcohol solution of bromine is not changed in both grafting system, until almost all the tyrosine is brominated to 3:5-dibromotyrosine. The graft-on, however, is sharply decreased when the oxidation of thiol groups must have occurred. The graft-on is not changed for silk fibers treated with absolute alcohol solution of bromine.
Acetylated wool has less graft-on because it has a lower concentration of persulfate inside the fibers compared with unmodified wool. Sharp decrease of graft-on for nitrated wool or silk seems to be due to the “retarder” effect of aromatic nitro compounds. By the treatment with diazomethane on wool fibers, the absorption of potassium persulfate is increased remarkably, but the graft-on does not change in the K2S2O8 system. From these results, it is suggested that graft copolymerization is initiated within the fibers by the free radicals which are formed by the action of the sulfate ion or hydroxyl radicals on thiol groups but not on tyrosine residues. Thus, the thiol groups in wool fibers have an essential role on the grafting and even though a large amount of persulfate is absorbed the grafting is limited by the content of thiol groups. These results lead to the same conclusion as that of the treatment with thioglycollic acid, alkyl halide after reduction, and potassium cyanide in our previous report. Inhibition of homopolymerization in the LiBr-K2S2O8 system is due to the bromination of monomers by liberated bromine. The liberated bromine will act to react with the easily oxidized component of wool or silk fibers. This consumption of bromine will contribute to proceed the graft copolymerization without homopolymerization regulating the bromination of monomers.抄録全体を表示PDF形式でダウンロード (678K) -
第1報 分子量の影響上出 健二, 稲本 義彦1967 年 23 巻 2 号 p. 79-85
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーThree kinds of polypropylene were melt spun using the straight die of 0.45mm diameter with 5mm length in the temperature range of 190 to 350°C at the rate of output 0.765cc/min. Details of the sample are following; Four fractions, ranging in molecular weight from 1.07×104 to 74×104 (I), five thermally degradated polypropylenes having molecular weight of 3.2×104 to 30.6×104 (II), of which the details of the preparation were described in the other paper (Kamide, Inamoto and Ohno; J. Chem. High Polymer, 22, 597 (1965)) and unfractioanted polypropylene (_??_=31.7×104) (III). Maximum draft ratio (MDR) is defined as the ratio of the linear velocity at the die-wall to that at the winding-wall, at which the continuous melt spinning becomes abruptly impossible. Relationship between MDR and spinning temperature (at die) (ST) closely depends on molecular weight (MW). Minimum MW having fiber formability is about 3×104 and in this case, the range of temperature suitable for melt spinning (RST) is extremely narrow (190±0.5°C). Although RST becomes wider with increased MW, RST becomes narrower again in the range _??_=40×104. Lower limit of ST, at which the continous melt spinning is possible becomes higher with increased MW. Most of the elongational deformation during the spinning ceases within 20cm. under the die, where the elongatioal viscosity is low. In the more deformed parts, the negligible orientation is observed by the birefringence measurement. The orientation may be attained after solidification and crystallization is completed. Since Poisson ratio of molten polypropylene estimated by using values of the compressibility and the Young's modulus is 0.5, the elongational viscosity at the outlet of the die is calculated as three times the shear rate viscosity (at the die-wall, shear rate is 103 sec-1 in this study), utilizing the results reported (Kamide, Inamoto, Ohno; J. Chem. High Polymer, 22, 529 (1965)) and assuming the apparent activation energy of melt flow of polypropylene as 8kcal/mole. Iso-elongational-viscous state was approximately attained at the optimum spinning temperature. when the temperature of atomosphere near the die is cooled, reduction of spinnability is observed at each spinning temperature, although the optimum spinning temperature does not change as far as the same sample was spun.抄録全体を表示PDF形式でダウンロード (548K) -
第1報 最高延伸倍率の分子量,分子量分布依存性上出 健二, 稲本 義彦, 藤井 清1967 年 23 巻 2 号 p. 86-92
発行日: 1967/02/10
公開日: 2008/11/28
ジャーナル フリーEffects of molecular weight and its distribution on stretchability of polypropylene fibers were studied in the temperature range between a room temperature and 140°C using undrawn filaments having molecnlar weights (MW) _??_=3.2×104_??_56.0×104 melt spun from fractions, thermally degradated, and unfractionated samples at spinning draft 50 (diameter and length of straight die used, 0.45mm and 0.5mm, respectively, the rate of output 0.765 cc/min, winding velocity 250m/min), at the optimum spinning temperature corresponding to molecular weight of each sample. Drawing was carried out at a fixed temperature with velocity 10cm/min in an oil bath by using the hand-drawing apparatus. The maximum draw ratio (MDR) is used as a parameter of stretchability, where MDR is defined as the draw ratio at which three-quarters of total filaments (20 filaments) brokes. The optimum draw temperature at which MDR is maximum is raised slightly with MW, however the temperature dependence of stretchability decreases with increased MW. Above 135°C, slretchability of filaments abruptly decreases except where filments have MW larger than 30.6×104. The increase in MDR of filament with draw temperature is attributed to the greater deformability of the whole crystalline region, which is suggested by the temperature dispersion of mechanical loss or thermal stress of filaments. Strechability of the sample having an extremely broad molecular weight distribution (MWD) (in this cnse, _??_=28) becomes larger than that having narrower MWD at temperatures lower than 100°C., and at temperatures above 100°C, however this tendency reverses. (MDR)max becomes maximum at _??_=5.4×104, which suggest that stretchability of filament is clogely related to the draining or disentanglement of the draining or disentanglement of the entangled chains in undrawn filaments.抄録全体を表示PDF形式でダウンロード (1112K)
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