巻号一覧
25 巻, 3 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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平林 潔, 石川 博, 角戸 正夫1969 年 25 巻 3 号 p. 103-106
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーA transparent solution was obtained by treating silk fibroin with dichloroacetic acid for one day at room temperature. The 1% solution gave cloudy precipitates by diluting with the same volume of water.
Needle-shaped crystals could be observed under optical microscope in the precipitates dried up on a slide glass at about 60°C.
The particles have sizes within the range of 0.5 to 5μ in width and 100 to 300μ in length.
Similar particles were also observed in the concentrated solution heated to 60°C. Fibrillar precipitates were obtained in more concentrated solution.
X-ray powder diagram of the fibrillar materials indicated presense of crystals with the extended β-configuration.
The fibroin film made from dichloroacetic acid solution were also identified as having the β-configuration by infrared absorption spectra showing the amide 1 band at 1625cm-1 and the amide II band at 1520cm-1.
The result of electron diffraction coincided with those obtained by other methods.抄録全体を表示PDF形式でダウンロード (2136K) -
渋沢 崇男1969 年 25 巻 3 号 p. 107-114
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーThe interaction between p-aminoazobenzene and anionic surfactants in aqueous solution was studied by spectral change of the mixed solution and decrease of equilibrium adsorption on dyeing of cellulose acetate in this system.
A p-aminoazobenzene molecule with an anionic surfactant molecule, such as sodium dodecylsulfate or sodium dodecylbenzenesulfonate likely forms 1:1-complex in aqueous soltion and a new adsorption band due to this complex spears at about 510mμ, while intensity of maximum adsorption of p-aminoazobenzene at 377mμ decreases.
Up to C. M. C. the new band increases in intensity with the concentration of anionics. The spectral change with a fixed concentration of p-aminoazobenzene and varying concentration of anionics has definite isosbestic point at 337mμ and 456mμ.
As the absorption of new band decreases with rising temperature, the formation of such complex is an exothermic reaction. There is little difference between the absorption spectra of the cellulose acetate film dyed in p-aminoazobenene aqueous solution in the presence and absence of anionics. From this results, it can be concluded that the complex itself is not taken up by acetate fiber, hence the formation of the complex in the dye bath leads to diminish the effective concentration of p-aminoazobenzene for dyeing.
The concentration of the complex in the infinite dye baths which contain different amount of anionics is determined from the decrease of apparent partition coefficient in acetate dyeing at different temperature. The equilibrium coefficients of the complex formation are thus determined at different temperature.
The heat of formation, ΔH° and entropy change, ΔS° of the complex formation between p-aminoazobenzene and sodium dodecylsulfate are caluculated to be -11Kcal/mol, -25cal/mol/deg, respectively. As the equiliblium coefficients of the complex formation are in the order of 102 at room temperature and pH=6.4_??_6.6, only a small amount of complex may exist in the dye bath at pratical dyeing temperature.抄録全体を表示PDF形式でダウンロード (538K) -
三軒 齊, 山本 吉威, 今村 力造1969 年 25 巻 3 号 p. 115-121
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーCondensation block copolymer composed of polyethyleneglycol (PEG) as flexible amorphous part of chain (soft segment) and aromatic polyetherester as crystallizable part of chain (hard segment) is elastic and can be melt-spun because of containing no crosslinkage.
Although the synthesis of block copolymer by using polyethyleneterepthalate (PET) as hard segment has previously been reported by Charch and Shivers, their investigation has not been extended beyond the general information regarding the effects of the composition of block components and chain length of used PEG (soft segment) on properties of block copolymer.
The primary purpose of this work is to investigate further properties of this block copolymer and its melt-spun fiber, and the second purpose is to study how replacement of PET by B (polyethylene-1, 2-diphenoxyethane-p, p'-dicarboxylate) as polyester component affect properties of block copolymer and its melt-spun fiber.
The results are summarized as follows.
(1) B-PEG type block copolymer somewhat surpassed T-PEG type block copolymer with regard to the degree of crystallinity and melting point. This fact may be interpreted as indicating that a unit chain length of B type polyester is about twice as large as that of PET polyester. On the contrary, the softening temperature of T-PEG copolymer is higher than that of B-PEG copolymer.
(2) As for the mechanical properties of melt-spun fibers, no marked differnces were observed in tensile strength and tensile elongation between the fiber of T-PEG and that of B-PEG, but T-PEG fiber has somewhat lower Young's modulus and a little higher elastic recovery than that of B-PEG. T-PEG fiber has still somewhat high Young's modulus and a little lower tensile recovery than elastic polyurethan fiber.
(3) Stress-strain curves of melt-spun fibers of these block copolymers display the Mullin's effect and stretched fiber exhibited inherent diffraction patterns of each homopolyester (B or PET) on X-ray diagram.抄録全体を表示PDF形式でダウンロード (1201K) -
高橋 利禎1969 年 25 巻 3 号 p. 122-127
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーIn the first paper on this series attention has been drawn to the selective uniplanar orientation of (101) planes in films. The purpose of this work is to investigate the above orientation of (101) planes in fibers. In order to determine whether preferencial orientation of (101) planes takes place or not, the micro X-ray examination were carried out on model bristles. These specimens having a diameter of 300_??_700μ were prepared by extruding viscose into several kinds of spinning baths through a glass nozzle. The thickness of cross-sectioned specimen was 30_??_50μ. Diffraction patterns were taken for several cross sections of undrawn and drawn bristles on different radial regions. The collimeter diameter was 50μ in each case.
No preferred orientation of (101) planes is observed in Toramomen type filament. It may be concluded that crystallites lie in all possible directions in this case, since the micro X-ray diagram agrees with the powder pattern. On the other hand, in the case of undrawn Müller type filament it is confirmed that the (101) planes have a preferencial orientation parallel to the fiber surface in a skin region, while random orientation in a core region. The degree of orientation becomes more pronounced with increasing sulfate in the bath. This orientation behavior is essentially identical with that described on films in the previous work of this series.
Undrawn Müller type cellulose filament exhibits smaller tangential and longitudinal swelling by wetting, and shrinkage by drying than Toramomen type filament. It seems reasonable to explain swelling properties on the basis of the preferred orientation of (101) planes parallel to the filament surface as in the case of films, keeping in mind that hydroxyl groups concentrate mostly on the (101) surfaces of cellulose crystallites. Fiber can be considered as the structure made from films concentrically multi-layered. Irregular shapes of cross section of viscose rayons, depending on the spinning bath, are discussed in relation to the preferencial orientation of (101) planes and anisotropic swelling and shrinkage behavior.
The change of the orientation of (101) planes with drawing are also examined by the micro X-ray method. The filament has a tendency to maintain the selective uniplanar orientation in spite of tangential decrease in dimension. This tendency is in good agreement with that found for drawn cellophane.抄録全体を表示PDF形式でダウンロード (3288K) -
高橋 利禎1969 年 25 巻 3 号 p. 128-132
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーPrevious work in this series has shown that preferential orientation of (101) planes of cellulose crystals parallel to a film surface was produced by strong dehydration during coagulation and regeneration process. The object of this paper is to describe the mechanism of such orientation of (101) planes in more detail.
Although the preferential uniplanar orientation of specific crystallographic planes of polyvinylacohol, cellulose, polyethyleneterephthalate and the like are familiar, but little attention has been paid to the mechanism of the orientation process. Some explanations have been given to each case in different terms; the conformational structure of molecular chains for polyvinylalcohol, the shape of crystallites for cellulose, and slipping and twinning in crystals for polyethylene respectively.
In the case of cellulose it is difficult to interpret on the basis of the molecular conformation in crystals, where the larger planes of anhydrous glucose units orient themselves almost perpendicular to a film surface, in contrast to the case of polyvinylalcohol, where the planes of planar zigzag molecular chains orient themselves parallel to a film surface. Alternatively, slipping and twinning mechanism in cellulose crystals is not likely a possible one, because of the extremely strong intermolecular forces compared with polyethylene. Finally, the shape of crystallites can not also be a reasonable factor to cause the orientation, since it is observed here by x-ray analysis that cellulose crystallite is a rod with a cross-sectional dimension of about 50 by 50Å, instead of a lamella or ribbon-like.
Then the orientation of (101) planes must be interpreted on the basis of some other different mechanism than those mentioned above. It seems reasonable to assume that absorbed water may plasticize cellulose crystallites and make them glide to each other on their (101) surfaces, considering the fact that most of the hydroxyl groups of cellulose molecules locate on these surfaces.
These assumptions may be supported by the following observation; the orientation of (101) planes take place only when swollen cellulose is compressed. If cellulose crystals deform through gliding on (101) surfaces, they undergo a rotation which brings these planes more nearly parallel to a film surface.
It would be difficult to interpret the preferencial orientation of (101) planes in terms of the fringed micelle moeel, where crystallites behave possibly as cross-links embedded in an amorphous matrix. Deformation of cellulose xanthate gel wonld be interpreted in the same way: the intermolecular forces are weakened by xanthation of hydroxyl groups, and gliding or slipping in crystals would be able to take place.抄録全体を表示PDF形式でダウンロード (398K) -
黒崎 新也, 近田 富士雄, 伊藤 元貴1969 年 25 巻 3 号 p. 133-140
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーIn the present study, an apparatus for the continuous measurement of the size and the interval of fiber assemblies flying at a high-speed air flow was first devised and its performance was investigated. Further, as an example of applying it in practice, the behavior of assemblies was measured by separating a sliver continuously by suction.
It is believed that by developing this study further, the basic information will be obtained on the clustering condition of fibers, which is importont in the pneumatic spinning, pneumatic conveyance, carding, etc.
The results obtained from this experiment are summarized as follows
(1) It is possible to measure the size of fiber assemblies flying with high speed by use of a capacitance type detector (Fig. 1).
(2) This apparatus enables one to detect a cluster composed of about 5-6 filaments of 3D, 2 in-cut viscose fiber.
(3) When a sliver, going out from the front roller after roller drafting is separated by suction, the intervals of separation is distributed nearly in accordance with an exponential distribution. The number of assemblies separated per unit time is subjected to a Poisson's distribution. The size of assemblies can be found from the average time intervals of the separation.
(4) The larger the roller draft ratio and the faster the suction speed, the more easily the sliver is separated into smaller assemblies.抄録全体を表示PDF形式でダウンロード (2040K) -
西田 健三, 大越 教男, 秋元 武博, 槌本 道子1969 年 25 巻 3 号 p. 141-143
発行日: 1969/03/10
公開日: 2008/11/28
ジャーナル フリーThe diazonium salts of aniline (I), p-toluidine (II), p-anisidine (III), p-chloroaniline (IV) and p-nitroaniline (V) were coupled with the anilide of 4-hydroxy-l-naphthoic acid (α). The absorption spectra, the solubilities for solvents and the light fastness etc. of the azo colours of a series of (α) were measured. Maximum absorption wave lengths (mμ) in toluene weve 500_??_504 ( (I)→(α)), 502_??_508((II)→(α)), 462_??_466 ((III)→(α)), 504_??_508 ((IV)→(α)), and 502_??_508 ((V)→(α)). These azo colours were slightly soluble in acetic acid, ethyl acetate, acetone or toluene, and very slightly soluble in methanol. Some of them gave a somewhat better light fastness than a series of colours from anilid of 3-hydroxy-2-naphthoic acid (β).抄録全体を表示PDF形式でダウンロード (124K)
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