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19 巻, 9 号
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Bengt G. Rånby1963 年 19 巻 9 号 p. 695-704
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーCellulose derives most of its functional properties from its hydroxyl groups: derivatives are formed by reactions with the hydroxyl groups, when cellulose is dissolved it is usually as a complex of the hydroxyl groups with ions or polar groups, and the physical properties of cellulose in the solid state are to a large extent a function of the hydroxyl groups.
It is known from infrared analysis that practically all hydroxyl groups in dry solid cellulose, both native and regenerated, are not free but engaged in hydrogen bonds of some kind. The proton donor group is always a hydroxyl group with another hydroxyl group or an oxygen group as acceptor. The accessibility of the hydrogen bonded hydroxyl groups has been measured by a combination of deuterium exchange (OH to OD groups) in heavy water and infrared analysis. Accessible OH groups are largely in amorphous (disordered) cellulose. The OH groups in crystalline (well ordered) cellulose are gradually made accessible by swelling with caustic soda solutions of increasing strength.
In regenerated cellulose a large fraction (usually about 80%) of the hydroxyl groups is accessible to the exchange in heavy water. Complete accessibility is obtained with 12 to 16% aqueous caustic soda. Intrachain hydrogen bonds along the cellulose chains are more resistant than interchain bonds between adjacent chains. By certain treatment the crystallinity of regenerated cellulose can be increased substantially. It has been found that the packing density of amorphous cellulose also can be increased by these treatments. Special crystallization processes from dilute solution give cellulose crystals of high order and low accessibility.
Native cellulose has a morphology of rather well defined microfibrils, containing parallel and partly crystallized cellulose chains. The accessibility is usually much lower (30 to 50%) than in regenerated accessible, we calculate an accessibility value for holocellulose from spruce of about 57%. Reported accessibilities for purified wood pulp from softwood are about 58% (8). If our measured data are accepted as given here, they would indicate that hemicellulose in the native state in wood, although X-ray amorphous, is only partially accessible to tritium exchange in tritiated water. There are, however, some difficulties in the interpretation of these measurements, and the data will be further treated elsewhere.抄録全体を表示PDF形式でダウンロード (1202K) -
第5報 孔数の多い紡糸口金について神谷 卓郎, 広川 完二, 今田 稔穂1963 年 19 巻 9 号 p. 705-712
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーWith the intention of increasing the production capacity of each spinning cell, an investigations has been made into the following subjects from a practical point of view; How to arrange the holes on the spinnerette in order to increase the number of holes, and the structure of the spinning cell.
The results obtained are as follows:
(1) A 3-stage supply of air into the spinning cell is suitable.
(2) The distance between each hole on the spinnerette should be more than 1.4mm,
(3) Using a spinnerette with 300 holes ranged in 4 concentric circles, each hole having a diameter of 0.06mm., 3d fibers are obtained without any fiber breakage when the spinning velocity is 500m/min.
(4) Using a spinnerette with 400 holes ranged in 4 concentric circles, each hole having a diameter of 0.06mm., 3d fibers can be spun, when the spinning velocity is 500m/min.
(5) Using a modified spinnerette with 500 holes, each hole having a diameter of 0.06mm., 3d fiber can be spun when the spinning velocity is 430m/min.抄録全体を表示PDF形式でダウンロード (565K) -
竹田 弘, 渡辺 正元1963 年 19 巻 9 号 p. 713-717
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーAn acrylic fiber, which is produced by wet spinning in the solvent-water coagulation system, is investigated in order to find out the influence of drying conditions on homogeneity in microstructure and mechanical properties of fiber. Mechanical properties of fiber can be changed by drying temperature and degree of relaxation. By drying in relaxed state, tensile strength of fiber changes a little, but tensile elongation and knot strength increases. Homogeneity in fiber microstructure increases by drying at high temperatures.抄録全体を表示PDF形式でダウンロード (2058K) -
竹田 弘, 渡辺 正元1963 年 19 巻 9 号 p. 717-723
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーAn acrylic fiber was investigated in order to find out the effects of steam and hot water treatment to mechanical properties of fiber.
Mechanical properties of fiber vary by the degree of relaxation during drying or heat-set. Homogeneity in fiber-microstructure increases by steam or hot water treatment. Stress-strain behavior of fiber is susceptible to temperature.抄録全体を表示PDF形式でダウンロード (2470K) -
斎藤 正雄, 笠井 忠夫1963 年 19 巻 9 号 p. 724-730
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーTwo kinds of regenerated cellulose fiber, high tenacity rayon and polynosic fiber, pretreated in our unique way, were acetylated in fibrous form with sulfoacetic acid catalyst. Results obtained-are as follows:
1. In the presence of free sulfuric acid in the acetylating liquid, high tenacity rayon is hardly acetylated, while polynosic fiber can be acetylated.
2. Impregnated additionally with dioxane or ethanol, the pretreated high tenacity rayon is still kept active toward acetylation. Impregnation with benzene, however, completely removes its reactivity.
3. Impregnated with solvents containing free sulfuric acid the pretreated high tenacity rayon decreases much more in its reactivity than by impregnation with the solvents without sulfuric acid.
4. Impregnated with acetic acid containing sulfuric acid, sulfoacetic acid, perchloric acid or zinc chloride, the pretreated high tenacity rayon unexceptionally decreases in its reactivity.
On the other hand the pretreated polynosic fiber in some cases increases in its reactivity.抄録全体を表示PDF形式でダウンロード (580K) -
第7報 酸加水分解残渣のカセイソーダ分別溶解機構と同法によるミセルの微細構造の検討西村 博, 中尾 統一, 鈴木 正幸, 右田 伸彦1963 年 19 巻 9 号 p. 731-738
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーHydrocelluose from various commercial dissolving pulps by preethanolysis for 30 minuites with 1N-HCl in absolute ethanol at the boiling point and successive hydrolysis for 30 minuites with 3.5N aq. HCl solution in a boiling water bath, were fractionated according to the sedimentation velocity in water, that is according to the size of the hydrocellulose particles, as reported in the previous paper in this series. The fractions were subjected to the fractional dissolution with aq. NaOH solutions of various concentrations at 7.6°C, in order to investigate the influence of the size of the particles on their solubility. Among the particles from a pulp, smaller particles never gave lower solubility, however smaller particles gave not always higher, but almost the same solubility in many cases. Thus, it is estimated that, in case of native cellulose micells, the fractional dissolution proceeds mainly on peeling off dissolution of the outer layer of each micell in according to the cohesive energy of each chain molecule, rather than on whole dissolution of each micell in accordance to the total cohesive energy of each micell. The fractional dissolution curves reflect strongly the mass-order distribution in the direction of width of the micell.
All micells in the pulps investigated have transitioal area in the direction of the width of the micell. The transitional area of the micells in the linters pulp consists of relatively highly ordered molecules, whereas it in the wood pulps consists of variously ordered molecules, and in the prehydrolyzed sulfate pulps it is of higher order than in the sulfite pulps. The micells in the beech pulps contain wider transitional area than those in the pine pulps. The linters pulp and the every wood pulp contain some smaller micells which are particularly rich in the transitional area, in addition to larger ones which are relatively poor in the transitional area and they form the majority.抄録全体を表示PDF形式でダウンロード (606K) -
第8報 酸加水分解によるミセルサイズ分布の変化西村 博, 中尾 統一, 右田 伸彦1963 年 19 巻 9 号 p. 738-743,732
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーA commercial viscose grade pine sulfite pulp and a cmmercial acetate grade linters pulp were hydrolyzed for various time with 3.5N-HCl aqueous solution in a boiling water bath with or without preethanolysis for 30 minuites with N-HCl in absolute ethanol at the boiling point, and followed the micell size distribution changes during hydrolysis by the fractional precipitation method in water given in the previous paper. The fractions obtained by the same method from the preethanolysishydrolysis residues were hydrolyzed again without drying, and the amounts and the reaction rate constants of highly ordered regions were determined in order to obtain information on the causes of the changes in the micell size distribution.
The smaller micells of the sulfite pulp, present originally in the pulp and are shows as a relatively large shoulder of the micell size distribution curve of hydrocellulose, obtained by hydrolysis for 30 minuites after preethanolysis, are hydrolyzed faster than other micells (Figs. 1 and 3, Table 1), It is due to the lower lateral order of chain molecules of the smaller micells as previously reported, because there is no relation between the size of micell and the rate constant (Table 1). The peak of the micell size distribution curve shifts towards lower degree of polymerization region with increasing time of hydrolysis, but even after the disappearance of the less ordered micells, the shorter micells, the lengths of which correspond to 100 or less in degree of polymerization value, do not increase (Fig. 3). This means that micells are decomposed being shortened by hydrolysis at their surfaces and by reaching the length. However the fractions of hydrocellulose obtained by hydrolysis for 5 hours after preethanolysis have the same rate constant (Table 1). It is obvious that hydrolysis proceeds also among the other larger micells resulting in disappearance, of much more micells and shortening of micell to the length is not always necessary for its decomposition.
The micell size distribution curve of linters pulp shifts a little, without change in form, with increased time of hydrolysis (Fig. 2), although the smaller and less ordered micells which are present in the early stage of hydrolysis have higher rate constant than in others (Table 1).抄録全体を表示PDF形式でダウンロード (627K) -
第9報 アルカリ浸せきによる微細構造の変化(2)西村 博, 中尾 統一, 管 益良, 島袋 徹, 右田 伸彦1963 年 19 巻 9 号 p. 743-750,732
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーA commercial viscose grade pine sulfite pulp and a commercial acetate grade linters, pulp were steeped in 4_??_18% NaOH solutione at 20°C, washed, dried, preethanolyzed for 1/2 hour with N-HCl in absolute ethanol at the boiling point, and hydrolyzed with 3.5 N-HCl solution in a boiling water bath successively. Micell size distribution curves of the presteeped pulps by fractional precipitation of the hydrocellulose after hydrolysis for 1/2 hour according to the sedimentation velocity in water, caustic fractional dissolution curves of the hydrocellulose fractions, leveling off degree of polymerization values of the hydrocelluloses after hydrolysis for 5 1/2 hours, and amounts and rate constants of highly ordered regions were determined in order to study the changes in fine structure with caustic pretreatment.
When the sulfite pulp is steeped in 6 or less percent caustic solutions, NaOH penetrates into the transitional area in the direction of the length of all the micells resulting in shortening of the lengths, but it penetrates only into the less ordered regions of the transitional area in the direction of the with. With increased caustic concentration to 8%, it penetrates almost to the cores of many of the micells destroying the original micells, and new shorter micells of various lengths regenerate after washing and drying resulting in distinct decrease of leveling off degree of polymerization and amount of highly ordered regions. In 10% solution, it penetrates to the core of all the micells, and results in regeneration of new further shorter micells of almost the same length and partial mercerization on X-ray diffraction.
In the case of the linters pulp, most of micells have no transitional area in the direction of the length into which NaOH can penetrate when that is steeped in 10 or less percent caustic solutions, but some micells have it and their lengths decrease a little due to penetration of NaOH in 8 and 10% caustic solutions. Whereas, the transitional area in the direction of the width suffers penetration in 8 and 10% caustic solutions resulting a little decrease of the amount of highly ordered regions. In 12% solution NaOH penetrates to the core of all the micells, and new short micells of the same length regenerate after washing and drying. As the results, leveling off degree of polymerizaton and amount of highly ordered regions decrease distinctly, and X-ray diffraction shows partial mercerization.抄録全体を表示PDF形式でダウンロード (719K) -
第1報 モデル染料の親和力,染色熱およびエントロピー変化について那須野 昭文, 五十嵐 良一1963 年 19 巻 9 号 p. 751-756
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーThe mechanism of dyeing of formalized vinylon with disperse dyes was studied, by using several vinylons having the degrees of formalization different from each other, and cellulose acetate rayon for comparison, and purified p-nitroaniline, p-nitrodimethylaniline, azobenzene and p-aminoazobenzene as models of disperse dves.
Isotherm curves, for the distribution of p-aminoazobenzene and p-nitroaniline between formalized vinylon and water, showed the linearities explained by partition law, and it was found that their slopes depend on the degree of formalization, namely, the higher formalized vinylon causes the higher partition coefficient of model dyes. Accordingly, it may be concluded that disperse dyes dissolve into formalized PVA substrate. Therefore, a correcting coefficient, a function of the degree of formalization, is introduced into Majury's equation to calculate affinities of model dyes on formalized vinylon.
Affinities of p-aminoazobenzene, p-nitroaniline and p-nitrodimethylaniline on vinylon, of which the degree of formalization was about 35 mole percent are nearly equal to those on cellulose acetate rayon. And also, their dyeing heat on vinylon are nearly equal to those on cellulose acetate rayon. But affinity and heat of the dyeling of azobenzene on formalized vinylon are lower than on cellulose acetate rayon, and its entropy changes of dyeing on formalized vinylon shows minus values, therefore it may be thought that other physical forces with exception of hydrogen honding are principal in this case.抄録全体を表示PDF形式でダウンロード (419K) -
第6報 染色濃度および色彩的性質におよぼすホルマール化の影響那須野 昭文, 田辺 健一1963 年 19 巻 9 号 p. 756-763
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーFurther experiment were carried out on the effects of formalization of vinylon under the various conditions of reaction, on the color-depths and color-shades of dyeings.
Heat-treated polyvinyl alcohol fiber is formalized under various conditions of reaction and the color depths and the color-shades of dyeings, and dyed with direct-color and disperse-color were measured with the following results:
As formalization proceeds the color-depths and color-shades of dyeings, dyed with direct-color, is generally found to increase initially and then decrease through maximum, on the other hand in the case the color-depth and color-shades of dyeings, dyed with disperse color, is improved with increase in degree of formalization.
The better color-depths and color-shades at the same degree of formalization of dyeings, dyed with direct-color, are obtained, the more swellable to fiber the condition of reaction with the formalization without sodium sulfate. On the other hand, the color-depths and color-shades of dyeings, dyed with disperse-color, are unrelated to the condition of formalization.
These results suggest that the deterioration of dyeing sites in the fiber decreases the degree of the color-depths and color-shades of the dyeing. This may be due to the variation in the existing state of dye in the fiber.抄録全体を表示PDF形式でダウンロード (557K) -
三浦 義人, 中条 芳之助, 鈴木 国夫1963 年 19 巻 9 号 p. 764-768
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーManufacturing condition of the nylon crimped single yarn is investigated. Twisting and heat setting are repeated three times, and the twisting at the first and the third times are limited on giving bulkiness. The temperature of heat setting should be kept lower than 130°C. At the point of strength, elongation and residual torque of the yarn thickness of hnitted fabric. etc., the desirable manufacturing conditions of the yarn are as follows.-
First process; 2000t/m twist, 120°C
Second process; 1500t/m over twist, 115°C
Third process; 150t/m over twist, 115°C抄録全体を表示PDF形式でダウンロード (2262K) -
平山 順之1963 年 19 巻 9 号 p. 769-774
発行日: 1963/09/10
公開日: 2008/11/28
ジャーナル フリーPDF形式でダウンロード (457K)
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