Cellulose and fiber science developments: A world view

Cellulose and Fiber Science Developments: A World View Jett C. Arthur, Jr., EDITOR Southern Regional Research Center, US...

Author: Jett C. Arthur | Jr.

271 downloads 910 Views 5MB Size Report

This content was uploaded by our users and we assume good faith they have the permission to share this book. If you own the copyright to this book and it is wrongfully on our website, we offer a simple DMCA procedure to remove your content from our site. Start by pressing the button below!
Report copyright / DMCA form

DOWNLOAD PDF

Cellulose and Fiber Science Developments: A World View Jett C. Arthur, Jr., EDITOR Southern Regional Research Center, USDA

A symposium sponsored by the Cellulose, Paper and Textile Division at the 171st Meeting of the American Chemical Society New York, N . Y . , A p r i l 5-9,

1976

ACS SYMPOSIUM SERIES 50

AMERICAN

CHEMICAL

SOCIETY

WASHINGTON, D. C. 1977

In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

Library of Congress CIP Data Cellulose and fiber science developments. (ACS symposium series; 50 ISSN 0097-6156) (Monograph publishing on demand : Imprint series) Includes bibliographical references and index. 1. Paper making and trade-Congresses. 2. CelluloseCongresses. I. Arthur, Jett C. II. American Chemical Society. Cellulose, Paper, and Textile Division. III. American Chemical Society. IV. Series: American Chemical Society. A C S symposium series; 50. TS1080.C414 ISBN 0-8412-0380-6

676 ACSMC8

77-22540 50 1-287

Copyright © 1977 American Chemical Society A l l Rights Reserved. N o part of this book may be reproduced or transmitted in any form or by any means—graphic, electronic, including photocopying, recording, taping, or information storage and retrieval systems—without written permission from the American Chemical Society. PRINTED IN T H E UNITED STATES O F AMERICA

American Chemical Society Library 1155 16th St. N. W In Cellulose and Fiber Science Developments: A World View; Arthur, J.;

Washington, D.Society: C. 20038 ACS Symposium Series; American Chemical Washington, DC, 1977.

ACS Symposium Series Robert F. G o u l d , Editor

Advisory Board Donald G. Crosby Jeremiah P. Freeman E. Desmond Goddard Robert A. Hofstader John L. Margrave Nina I. McClelland John B. Pfeiffer Joseph V. Rodricks Alan C. Sartorelli Raymond B. Seymour Roy L. Whistler Aaron Wold


FOREWORD The ACS SYMPOSIUM a medium for publishin format of the SERIES parallels that of its predecessor, ADVANCES IN CHEMISTRY SERIES, except that in order to save time the papers are not typeset but are reproduced as they are submitted by the authors in camera-ready form. As a further means of saving time, the papers are not edited or reviewed except by the symposium chairman, who becomes editor of the book. Papers published in the ACS SYMPOSIUM SERIES are original contributions not published elsewhere in whole or major part and include reports of research as well as reviews since symposia may embrace both types of presentation.


PREFACE he centennial meeting of the American Chemical Society gave the Cellulose, Paper and Textile Division the opportunity to present a timely symposium on International Developments in Cellulose, Paper, and Textiles. Research scientists from academia, industry, and government, representing more than sixteen countries, presented significant research accomplishments in paper, wood, and cellulose chemistry and in cotton, wool, and textile fiber chemistry. In this volume, worl ments are contributed in three areas—cellulose, paper science, and fiber science—by investigators from Australia, Canada, Finland, France, Japan, Mexico, Rumania, Sweden, and Switzerland. Two companion volumes, "Cellulose Chemistry and Technology" and "Textile and Paper Chemistry and Technology" include other contributed manuscripts. I would like to thank the participants and the presiding chairmen of the world views sessions» particularly R. R. Benerito, C. Schuerch, K. Ward, Jr., R. L. Whistler, and J. J. Willard. Herman Mark kindly made significant remarks to open the Symposium. Southern Regional Research Center, USDA New Orleans, L A May 11, 1977

JETT

C.

ARTHUR,

vii


JR.

1 Recent Research and Technological Development of Cellulose in Japan KEI MATSUZAKI Faculty of Engineering, University of Tokyo, Hongo, Bunkyoku, Tokyo, 113 Japan

Production of chemica Japan changed as shown rayon reached to a maximum in 1937-38 and decreased to one twent i e t h during and after the second world war due to converting of the factories to munitions manufacturing and destruction. From around 1950, the production rapidly increased and the total production of c e l l u l o s i c fibers is ca. 500,000 tons/year for these ten years. In the field of c e l l u l o s i c f i b e r s , several companies stopped production of viscose rayon filament yarn and high tenaci t y yarn for t i r e cord and the output of those fibers decreased, while the output of cellulose acetate fibers and viscose rayon staples increased. The manufacturers of c e l l u l o s i c fibers and cellulose derivatives in Japan are l i s t e d in Tables I and II. Investigations on cellulose were active in 1930's and also after the second world war, especially on rayon fibers of new type such as polynosics and high tenacity rayon for t i r e cord, pulps for cellulose acetate, and c r y s t a l l i n e and supermolecular structure of cellulose. Most of companies, however, now stopped basic and application researches on c e l l u l o s e , although a large number of researchers in universities continue to work on c e l l u lose, especially, in Hokkaido University, Gumma University, University of Tokyo, Tokyo Institute of Technology, Shizuoka Univers i t y , Tokyo Metropolitan University, and Osaka City University. The number of a r t i c l e s related to cellulose and published in Japanese journals is ca. 200 for these ten years. Most of them were published in Sen-i Gakkaishi(J. of Soc. of Fiber Science and Technology, Japan, o r i g i n a l l y published in 1925 as J . Cellulose Institute). Kogyo Kagaku Zasshi(J. Chemical Society, Japan, Industrial Chemistry Section) which was united to Nippon Kagaku Kaishi now , also published a large number of papers together with Kobunshi Ronbunshu(J. High Polymer Society, Japan), Japan TAPPI and Mokuzai Gakkaishi(J. Wood Research Society, Japan). In addition, a considerable number of papers are published in foreign journals. Japan Tappi was established in 1947 just after the war. 3


C E L L U L O S E A N D FIBER

Table

i.

Manufacturers

Viscose rayon

of Rayons and C e l l u l o s e Acetate

Fibers

filaments;

Asahi Chemical Toray,

Ind.,

Kuraray,

Toyo Spinning,

Viscose rayon filaments Unitica.

for

Toray,

Unitica.

Teijin

tire

cord;

Teijin,

Toyo Spinning.

Viscose rayon s t a p l e s ; Mitsubishi

Rayon, Kanebo,

Toho Rayon,

Toyo Spinning,

Kuraray,

F u j i Spinning,

Nisshin Spinning,

Nitto

Daiwa Spinning,

Spinning, Kojin,

0m1 Kens hi

Spinning.

Toray Cuprammonium rayon; Asahi Chemical Acetate

fibers;

Mitsubishi

Acetate,

Daicel,

Asahi Chemical

Ind.,

Teij i η . The underlined manufacturers indicate those which stopped the production.

Table

II.

Cellulose

Manufacturers

Cellulose

Derivatives

nitrate;

Asahi Chemical Ind., Cellulose

of

Daicel,

Taihei Chemicals.

acetate;

Daicel,

Teijin,

Carboxymethyl Daiichi

Asahi Chisso.

cellulose; Kogyo Seiyaku,

Nichirin

Kagaku,

Daicel,

Adachi Koryo,

Sanyo

Kokusaku Pulp,

Shikoku Kasei,

Kyoto Gosei Kagaku. Methyl

cellulose;

Shin-etsu Kagaku, Hydroxyethyl

Matsumoto Yushi.

cellulose;

Fuji Chemical. Hydroxypropyl

cellulose;

Nippon Soda,

Shin-etsu

Hydroxypropyl methyl Shin-etsu

Kagaku.

cellulose;

Kagaku.

Hydroxy ι propyl methyl c e l l u l o s e Shin-etsu

phthalate;

Kagaku.

C e l l u l o s e acetate

SCIENCE

phthalate;

Wako Junyaku.


1.

1936

5

Cellulose in Japan

MATSuzAKi

1940

1945

1950

1955

1960

1965

1970

1975

Figure 1. Change of production of rayons and cellulose acetate fibers

Table

III.

Year Kogyo Kagaku Ζasshi

Number of

Articles

Published

Gakkaishi

Kobunshi Japan

Kagaku

TAPPI

Journals

65

66

67

68

69

70

71

72

73

74

75

3

5

7

3

4

5

10

-

-

-

-

37

2

5

4

5

16

Nippon Kagaku Kai s h i Sen-i

i n Japanese

Total

23

22

26

8

11

11

5

6

3

25

1

119

3

3

0

1

2

2

4

4

5

3

1

28

0

1

0

0

2

0

5

1

3

0

1

13


6

CELLULOSE

A N D FIBER

SCIENCE

Main thema of the investigations are the followings: Crystalline structure of cellulose and cellulose derivatives. Folding molecular structure of cellulose. New solvents for c e l l u l o s e . Synthesis of new cellulose derivatives. Fire-retarding effect of cellulose phosphate and i t s deriva tives. Effect of gamma-ray i r r a d i a t i o n or UV l i g h t on c e l l u l o s e , such as change of molecular weight, esr spectra and proper ties of irradiated products. Grafting of vinyl monomers onto cellulose and i t s derivatives by gamma-rays, UV l i g h t or with chemical catalysts or in the absence of catalyst.

1. 2. 3. 4. 5. 6. 7.

Some of the topics w i l l be discussed in the followings. 1.

Crystalline Structur Watanabe and Hayashi of Hokkaido Univ. proposed that the conformation of cellulose I i s different from that of cellulose II and that the differences in the conformation and the s t a b i l i t y is the cause of preservation and irreversibleness of c r y s t a l l i n e structure of cellulose I and cellulose II. At f i r s t , the c r y s t a l l i n e structure of cellulose t r i n i t r a t e (TNC) was investigated(l_,2). They proposed approximately 5 hel i c a l structure with a fiber period of 25.75A for TNC, although cellulose d i n i t r a t e obtained in a homogeneous reaction has a c r y s t a l l i n e s t r u c t u r e with a twofold screw axis and a f i b e r p e r i od of 10.32A, same as other cellulose derivatives. Transforma tion of the twofold screw axis structure into 5 helical struc ture by t r i s u b s t i t u t i o n may be caused by twisting of pyranose ring in chair form to semi-boat form. The twisting may be re sulted by the bulkiness and repulsion between two nitro groups at 1*2 and Cg positions. The nitro groups which are o r i g i n a l l y in gauche conformation change into trans conformation. It was noted that natural cellulose always gives TNC with high c r y s t a l l i n i t y irrespective of sources, while cellulose II such as rayons even with high c r y s t a l l i n i t y ( F o r t i s a n ) gives TNC with low c r y s t a l l i n i t y ( 3 j . They proposed a bent-twisted structure which has no two fold screw axis for cellulose I I , as shown in Figures 3 and 4. Therefore, the structure of TNC obtained from cellulose II i s fundamentally 5 h e l i c a l , although i t i s incomplete(4). They analyzed c r y s t a l l i n e structure of cellulose II with the use of the bent-twisted conformation of molecule and obtained re l i a b i l i t y factor R = 0.265 for φ! =30° and φ =45° (5). This structure could explain i r spectra of cellulose II w e l l ; that i s , two intramolecular hydrogen bond absorptions due to 0j—>0ci> -CH symmetrical stretching vibration(parallel) and antisymmetrical stretching v i b r a t i o n ( a n t i p a r a l l e l ) . It i s well known that cellulose has cellulose III and IV modifications besides I and II. Mann et al.(6) found that OH v i 0

2

0

2

2

α

2


MATsuzAKi

Cellulose in Japan

O and Ο -» O are formed in (101 ) and (002) planes, alternatively. 2

e

β


s

8

CELLULOSE

A N D FIBER

SCIENCE

rations of cellulose III(or IV) change with the crystalline struc ture of cellulose(cellulose I or II) from which cellulose III(or IV) is derived. However, since X-ray diffractions are not clear ly different between cellulose III derived from cellulose I(designated as cellulose 1111 ) and that from cellulose II(cellulose 11111 ) , i t has not certainly been established that cellulose 1111 has a c r y s t a l l i n e structure different from that of cellulose

ιπ . π

Hayashi and Watanabe determined the ratio of meridional d i f fractions (040)/(020) on cellulose III and cellulose IV as shown in Figure 5(7j. The ratio changed with the c r y s t a l l i n e structure of source cellulose but not with the c r y s t a l l i n i t y or orientation of c r y s t a l l i t e s . Therefore, cellulose III ι(or cellulose IVl) is a c r y s t a l l i n e modification of cellulose different from cellulose 11111 ( or cellulose IV j j ) , although they show similar equatorial diffractions. Various chemical reactions on cellulose I usually produce cellulose 1111 or cellulose IVj, and we obtain cellulose 111jj and cellulose IVjj from cellulose II. Interconversion between cellulose I, 111j and IVj or that between cellulose II, Ι Ι Ι π and IVιj is possible, but conversion of cellulose I family to c e l lulose II family is only possible by dissolution and regeneration or mercerization(8), and i t is irreversible(Figure 6). In the est e r i f i c a t i o n such as acetylation and nitration or in the formation of addition compounds of cellulose I, molecular conformation of cellulose I is preserved and the regeneration results in cellulose

1(8-13).

The facts that the difference in molecular conformation is not reflected in equatorial diffractions as i l l u s t r a t e d in Figure 8 for cellulose t r i n i t r a t e , but reflected in meridional d i f f r a c tions as already mentioned were ascertained by calculating d i f fraction i n t e n s i t i e s . Thus, irreversibleness of cellulose I family to cellulose II family and preservation(or keeping memory) of each family struc ture during chemical reactions are caused by the molecular con formation of each family; that i s , the bent structure for c e l l u lose I family and the bent-twisted structure for cellulose II fam i l y . They are not due to difference in the intermolecular hydro gen bonding systeig. In cellulose I, the distance between H-| and H 4 ' is only 1.85 Α(Φ,=Φ =34°) by the intramolecular hydrogen bond between Οβ-^Ο^·. This form is very unstable. Formation of c e l l u lose II by twisting results in longer distance between H] and H 4 1 , thus giving a s t a b i l i z a t i o n energy of 2-3 kcal per glucose unit, which sums up to a large value for a molecule. It i s known that mercerization is a typical reaction of con version of cellulose I to cellulose II in fiber form. Merceriza tion of cellulose I under r e s t r i c t i o n of contraction or at high temperature to prevent swelling gives Na-cellulose I with ratio of meridional d i f f r a c t i o n s , (040)/(080) = 0 . 5 , whereas that of Na-cellulose I obtained from cellulose II is 0.02-0.05, irrespecΖ


Cellulose in Japan

MATSuzAKi

Figure 4. Crystalline structure of cellulose II. Projection to (10Ί) plane. (-*) Hydrogen bonds in (101) plane; (=5) hydrogen bonds in (002) plane.

(040)

J

10

1

I

20

1

I

30 2 Θ (°)

I

(040)

I

I

40 10

I

I

I

20 2 θ

1

30 (·)

1

L

40

Figure 5. Crystalline modification of cellulose and meridional diffractions. R indicates the ratios of (020) to (040).


10

A N D FIBER SCIENCE

family I | family Π Meridional Diffract. Π TYPE I.HIi TYPE

/mJ

LU Û_ >\~

«

1

Figure 6. Transformation be tween cellulose modifications and classification of crystalline struc tures of cellulose based on the conversion

UNIT CELL (Equatorial Diffract)! I TYPE 1

CELLULOSE

Γ* Trinitrate I

Cell m

H Dinitrate I tiHCellll pTriacetatel

Cell I

Figure 7. Change of crystalline structure of cellulose in esterification in fiber j—HCelllEn form. ( ) Transformation of crystalline structure; ( ) heat-treatment Celinh Celll^ or swelling.

J Trinitrate Π -J

n

J

H Dinitrate π}-|^ C e l l l pTriacetatel p


1. MATSuzAKi

Cellulose in Japan

11

tive of the mercerization conditions(14). Therefore, there are two types of Na-cellulose I, that i s , Na-cellulose:Ii and Na-cellulose I χ χ . Although usual procedure for regeneration of Na-cel lulose Ij gives cellulose II, regeneration under l i t t l e swelling such as with hot water or with acetic acid gives cellulose I as i l l u s t r a t e d in Figure 9 for ramie. Na-cellulose I T is formed in the condition that cellulose is not strongly hydrated. Therefore, i t is deduced that for conversion of cellulose I conformation to cellulose II conformation, strong hydration of cellulose chains is necessary to give relaxation to intramolecular hydrogen bond ings. Therefore, mercerization or regeneration of Na-cellulose under strong swelling gives always cellulose II type structure. 2.

New Solvents for Cellulose

Recently, various kind l i q u i d N2O4 added with a l i t t l e amount of organic compounds by Fowler et a l . ( 1 5 ) , dimethyl sulfoxide(DMSO) added with a small amount of N0O4 by Williams(ll5) » pyridine-anhydrous chloral by Meyer(V7L liquid SO2 added with a secondary or tertiary amine by Hata et a l . ( 1 8 j , and dimethyl formamide(DMF) or dimethyl acetamide(DMAc) added with N2O4 or N0C1 by Schweiger(19-20). Nakao et al.(21,22) developed previous investigations in de t a i l as shown in Table IV and found several new solvents. They c l a s s i f i e d cellulose solvents into the following groups: (i) DMSO, DMF,DMAc and ethyl acetate added with a l i t t l e amount of N2O4. ( i i ) DMS0,DMF, formamide, a c e t o n i t r i l e , methylene chloride, e t c . , added with 3-30 moles of l i q u i d S02~amine(e.g., d i e t h y l amine) complex. ( i i i ) DMSO, DMF, DMAc and N-methyl-2-pyrrolidone added with an hydrous c h l o r a l . (iv) DMSO, DMF, DMAc and pyridine added with N0C1, or l i q u i d N0C1 added with a l i t t l e amount of polar organic solvents. Solvents such as DMSO and formamide added with S02-amine com plex, or DMSO, DMF and pyridine added with N2O4 not only dissolve cellulose in a few minutes, but the solution is stable and degra dation of cellulose is low especially at low temperatures lower than 50°C. The dissolution proceeds by cleavage of fibers and peeling-off from the fracture surface without appreciable swell ing usually observed in dissolution by aqueous solutions such as cuprammonium solution. It is also noted that at least 3 moles of reagents per glucose unit are necessary for dissolution of c e l l u lose. Solvents added with S02~amine complex were investigated in detail(22). Thirty four solvents were found to dissolve natural cellulose but did not dissolve regenerated cellulose. The spec i f i c conductivities of complex solutions and cellulose solutions were determined, and the mechanism of dissolution was investiga ted. The complex formed between an amine and SO2 reacts with e e l -


12

CELLULOSE

Table

Cellulose sol vent

IV.

Solvents

SOg-amine

f o r Dissolving

Μ

g

r+ Ο φ —• 3 Φ

Sulfoxide Amide

DMSO DMF

Φ

3

TD

20

3 DMSO 50 14 DMF

DMAc

50 14 DMAc formamide 20 3 di ethyl Lactam

20

N0CU g

ο 3 — •σ Φ

Chloral

Φ

ο — φ

3 DMSO 3 DMF

_

n- 3 Φ ο 3 —

T3 Φ

3 DMSO 20 10 DMF 20

20 5

20 10 DMAc

20 10 20 10

5

^-butyro- 5 1actam £-capro1actam

Ami ne

50 30 pyri di ne 20 35

Nitrile

acetoni tri 1 e

pyri di ne 20 4 pyri di ne d - p i c o l i ne•20 5 3 - ρ i c ο 1 i η.20 e 7 20 15 acetoni t- 20 35 [aceto ri1e ni t r i 1 e ]

propionitrile

50 15 propionitrile

benzoni tri 1 e

50 25

Ester

50

ethyl acetate

methyl formate Lactone

Cyclic carbonate

5 [propi onitrile] [benzyl ni t r i l e ]

20

methyl 20 propi onat e

[

Cellulose.

20 20 5 DMAc 20

A N D FIBER SCIENCE

5 [ethyl acetate] 5

2C 8

f-Valero1 actone

50 20

/ - v a l ero- 5C 8 1actone

ï -butyro1actone

50 40

^-butyro- 5C 8 1actone

ethylene carbonate

50 30

propylene 5C 1 carbonate

propylene carbonate

50 30

] indicates

1iquid N0C1 .

mole i n d i c a t e s moles of reagents

per g l u c o s i d i c

# i n d i c a t e s cellophane is s o l . , but wood pulp is

unit. insol.


f

20

5

1. MATsuzAKi

13

Cellulose in Japan

l u i ose resulting three component complex of type II or III. The i r spectra of the cellulose solution is only overlapping of amineSO2 complex and c e l l u l o s e , and the absorption of OH groups of c e l lulose remains intact. Therefore, the formation of -0-S- bonds as is shown in IV or V i s not considered. Cell-OH

C e

ll-0

+ RN 3

H

SiC'

0

Cell-0-S0 H

Cell-0

2

+ R^H

+

S0

2

(IV)

(III)

Possible applications of new solvents of cellulose are investigated to some extent and suggested. (i) New solvents can dissolve blends of cellulose and synthetic polymers such as p o l y v i n y l chloride), polystyrene, polyacryl o n i t r i l e , etc. Blends of cellulose with cellulose acetate or cellulose nitrate are also dissolved. Films formed from blends of cellulose and poly(alkyl acrylate) are transparent and soft without addition of p l a s t i c i z e r . ( i i ) Grafted cellulose with vinyl polymers can be dissolved in the new solvents. Starch grafted with vinyl polymers also d i s solves. ( i i i ) Synthesis of cellulose derivatives with high degree of subs t i t u t i o n or homogeneous distribution of substituents w i l l be possible in the reaction in a homogeneous phase(e.g., synthesis of secondary cellulose acetate in one step). (iv) Production of f i l m s , f i b e r s , etc. from organic solutions of c e l l u l o s e , or blends, or grafted cellulose was suggested. It i s expected that those products may have special properties. 3.

Synthesis of Cellulose Derivatives

Synthesis of Unsaturated Acid Esters of Cellulose. General methods to synthesize cellulose esters are: (i) to treat cellulose with acid anhydride or acid chloride in the presence of a catalyst such as s u l f u r i c acid, perchloric a c i d , zinc chloride, or sodium acetate, or ( i i ) to treat cellulose with a mixture of the acid and t r i f l u o r o acetic acid anhydride or chloroacetic acid anhydride in the pres-


14

CELLULOSE

A N D FIBER

SCIENCE

ence of a catalyst. In our investigations(22,24) on the reaction of mixtures of α , β - u n s a t u r a t e d acid and acetic acid anhydride with c e l l u l o s e , i t was found that the substitution of unsaturated acid and acetic acid depends on the catalyst and the dissociation constants of the unsaturated acids. When s u l f u r i c acid i s the catalyst, strong acid such as ac r y l i c acid i s not introduced, whereas weak acids such as 3 , 3 dimethylacrylic acid are introduced more than acetic acid. In Table V, the results of e s t e r i f i c a t i o n of l i n t e r pulp(cellulose acetate grade) are shown. It shows that the ratios of unsaturat ed acid to acetic acid depend mainly on the pK of the unsaturat ed acids and do not depend on the composition of the mixed acids for e s t e r i f i c a t i o n . Rayon staple fibers treated with 40% potassium acetate as the catalyst were e s t e r i f i e dride, an unsaturated acid and potassium acetate in toluene at 120°C for 1-30 minutes. The results are shown in Figure 10. When the composition of cellulose mixed esters treated with the mixed acids of the same composition, e . g . , unsaturated acid/ace t i c acid anhydride = 1/1(by weight) is compared, i t i s seen that a c r y l i c acid is introduced more than 3,3-dimethylacrylic acid. This is quite opposite to the e s t e r i f i c a t i o n with s u l f u r i c acid as the catalyst. The relationship is shown in Figure 11. When s u l f u r i c acid i s the catalyst and the unsaturated acid is a stronger acid than acetic acid, the unsymmetrical anhydride formed by the reaction of the unsaturated acid with acetic acid anhydride, dissociates into an acetoxyl cation and an unsaturat ed acid anion. The acetoxyl cation produced mainly reacts with cellulose resulting in almost pure cellulose acetate. When the unsaturated acid is a weaker acid than acetic acid, such as β , β dimethylacrylic a c i d , dimethylacrylic acid cation i s mainly pro duced and attacks c e l l u l o s e . With potassium acetate as the catalyst, the dissociation of anhydride may be supressed by the presence of a large amount of s a l t and a nonpolar solvent(toluene), and the unsymmetrical anhy dride may d i r e c t l y be concerned with the e s t e r i f i c a t i o n . In this case, the composition of mixed acids affects the composition of cellulose esters, because the e s t e r i f i c a t i o n by acetic acid anhy dride and unsaturated acid anhydride also occurs and the ratio of the two anhydrides changes with the composition of the mixed ac ids. CrkCO. . CH C0 a

Q

CH = CHC00H 2

CH C0 CH =CHC0 3

+

C H 3

3

C Q

.°

v

CH -CHC0-°

V -

+

2

CH C0 3

C

H

3

CH =CHC00" 2

2


C

0

0

H


of

acid

56.0 46.7 48.0

0.8

acid

11.9

7,9

cellulose

„

b:

a

f \^

a

r « lb

a:

3,3-Dimethylacrylic acid

Crotonic

2g,

„

unsaturated

50.1

0.9

a

2g,

6.7

58.8

0.26

r

0.64

58.6

0.25

f \ lb

0.142 2.82 2.75

49.9 11.1 10.25

52.1 47.0

a c i d 0.4 m o l e s , 0.28

10.0

acid

anhydride 0.16 moles, 0.28

0.193

13.5

48.8

0.0941

0.0089

0.0103

(mol/mol)

acetic

2

a

o

f

4

0 . 2 nrl . 0.2 ml

5.12(25°C)

4.69(25°C)

4.43(25°C)

4.25(25°C)

H S0 2

K

acid

p

4

Anhydride

H S0 )

unsaturated acid

(cat;

and A c e t i c

0.028

52.7

60.0

59.8

acid(wU)

acetic

acetic

5hr

an U n s a t u r a t e d A c i d

59.1

2.1

0.74

acid(wU)

acid(wt%)

a

of

unsaturated

with Mixtures

acid(wt%)

2hr

Cellulose

acetic

of

unstaturated

Methacrylic a c i d
acetone>dioxane. The kind of vinyl monomers affected the radical decay in the order, methacrylic acid >methyl methacrylate = styrene. The rate of radical decay i s related to the a f f i n i t y of the solvents to cellulose fibers and the rate of penetration of solvents into f i b e r s . The preirradiated samples are capable of i n i t i a t i n g the graft copolymerization, while the unirradiated sample is not at a l l . Therefore, i t is concluded that the a b i l i t y of the samples preirradiated at room temperature to i n i t i a t e graft copolymerization is attributable to the cellulose radicals stable at room temperature. These radicals showing a singlet spectrum are believed to be alkoxy radicals at either C] or C4 position of the glucose unit resulted by the scission of glycosidic bonds. In order to verify the formation of alkoxy radicals by s c i s +

+

+

+


22


_

S

S ο

120 100 80 60 AO

0

UT

1

R] 0]

UT

.1500

SCIENCE

R

2

0

2

R

0

3

R^

Ο4

R

2

0

2

R3 0

3

R4

O4

0

2

R

0

3

3

> 1000

Figure 18. Changes of mechanical erties of BIED-treated cotton fabrics by reduction and oxidation treatments. (A) Content of SS linkages; (B) flex abrasionS 300 ο 200resistance (untreated cotton 1880 cycles); (C) breaking strength retention; (D) i 100 0 warp wrinkle recovery, (O) dry, (Φ) < wet. (U) Untreated, (T) BIED-treated; (R) reduction, (O) oxidation.

U

Τ

R

1

0

1

R

2

3

TREATMENTS

2 min

10 min

30G

Figure 14. Decay of ESR spectra by warming the sam ples to room temperature and recorded at 77°K. (A) Wood cellulose irradiated with high-pressure mercury lamp for 60 min at 77 °K; (B) Fe -sensitized wood cellu lose irradiated with high-pressure mercury lamp for 60 min at 77 °K; (C) Fe -sensitized wood cellulose irradi ated with super high-pressure mercury lump for 90 min at77°K. 3+

3+


O4

1.

Cellulose in Japan

MATsuzAKi

TaWeVI

Reaction

of

Cotton

23

with

BIED

Branch

R e a c t i on

Total

time(hr)

combi ned (ccmoles/g)

BIED

Cross-

E f f i ciency

links ( i^mol es/g)

(%) 50

1

110

55

55

5

207

88

119

57

10

267

110

157

58

24

303

153

250

49

48

404

209

195

48

Table VII,

Mechanical

properties

of m o d i f i e d cotton

fabrics Breaki ng

Warp w r i n k l e

Sample

Treatment

SH

SS

(^tmoles/g )

recovery

strength

angle

retention (%)

dry

wet

Untreated

76

44

100

DMF-treated

72

46

99

73

47

97

104

111

57

reduced

II

-

BIED-treated •

0

reduced

733

0

70

67

73

23

328

lo9

115

48

oxidized

II

TableVffl. R e l a t i v e

signal

484

intensities

of c e l l u l o s e samples

i r r a d i a t e d with hi gh-pressure mercury

lamp at room

temperature.

Relative Sample

Number of s c i s s i on s ,

signal

i ntensi t y , a r b i t r a r y

units

mmole X

Untreated

1.0

Oximated

0.8

2.7

0.6

Swollen

3.0

4.2

11.5

3.1

9.0

15.3

Fe

+3

a:

sensitized

hard g l a s s , i r r a d i a t i o n

b: quartz

3.1

a

b

1.0

10

3

time 60 min.

glass, irradiation

time 30 min.


14.2 10.4

-

b

24

CELLULOSE

A N D FIBER

SCIENCE

sion of glycosidic bonds, cellobiose as a model compound of c e l lulose was irradiated with l i g h t of wave length longer than 2800 A at 77°K for 2 hr. The esr spectra of the irradiated cellobiose and cellulose(soft wood dissolving pulp) are shown i n Figure 16. No radicals were detected on glucose under the same irradiation conditions. With l i g h t of wave length longer than 2200 A, r a d i cals were formed on glucose, but the intensity was much stronger for cellobiose as shown in Figure 17. The reason for higher ac t i v i t y of cellobiose toward l i g h t than glucose i s attributed to the glycosidic bonds in the molecule. Paper chromatographic analysis of cellobiose irradiated with l i g h t of wave length longer than 2200 A at room temperature showed the presence of glucose. Figure 18 shows the esr spectra of cellulose samples treat ed with Ce+4, F e , Fe 3, and A g , and irradiated with a super high-pressure mercury lamp at 77°K for 90 minutes. Although there is a small differenc t i z e r s , i t is considered that their effects are nearly the same as those of Fe 3. Namely, these sensitizers contribute to the formation of radicals showing the singlet and t r i p l e t spectra. In the irradiation in a i r , hydroperoxide is generally form ed and the grafting reaction occurs by the decomposition of the hydroperoxides. We found, however, that hydroperoxide is not produced in the irradiation of cellulose in the air(43). The hydroperoxide of cellulose may be unstable and decompose rapidly into stable compounds. Therefore, in the graft copolymerization by the preirradiation in the a i r , the grafting occurs at trapped radicals as in the grafting in vacuum. It is noted that cellulose acetate forms hydroperoxide by the irradiation in the a i r and the degree of grafting and the total conversion of vinyl monomer(styrene) are proportional to 1/2 power of the concentration of hydroperoxide. Therefore, the grafting occurs at hydroperoxide groups formed in cellulose ace tate, although the i n i t i a t i o n efficiency is low. 0

+ 2

+

+

+

1

(2) Composition of Grafted Polymers(Branch Polymers). Grafting reaction is very often carried out in heterogeneous phase, espe c i a l l y in the reaction onto cellulose. In the heterogeneous grafting, when mixtures of vinyl monomers are grafted onto a trunk polymer, the monomer reactivity ratios π and r2 may be different from those in the ordinary copolymerization in l i q u i d phase. Sakurada et al.(44J investigated on the grafting of mix tures of styrene-acrylonitrile and butadiene-acrylonitrile onto viscose rayon. Odian et al.(45) investigated on the grafting of styrene-acrylonitrile onto cellulose acetate. In our i n v e s t i g a t i o n ( 4 3 j » mixtures of styrene-butyl acrylate were grafted onto viscose rayon and cellulose triacetate fibers. The comparison of the monomer reactivity ratios in the grafting with those in the ordinary copolymerization indicated that sty rène is contained in the grafted polymer more than in the ordinary copolymers, as shown in Table IX. The cause was explained by


Cellulose in Japan

MATSuzAKi

ω 0

ifc

20 30 40 TIME (min)

50

60

Figure 15. Effect of various solvents on the decay of radicals produced by irradiation at room tempera ture. The F e *-sensitized sample was irradiated at room temperature for 30 min in quartz system. 3

Figure 16. ESR spectra of cellu lose and cellobiose irradiated with light of > 2800 Aat77°K


CELLULOSE

0

A N D FIBER

' IRRADIATION TIME (min)

Figure 17. Formation of radicals in glucose and cellobiose by irradiating with light of > 2200 A

Figure 18. ESR spectra of sensitized samphs irradiated with a super high-pressure mercury lamp at 77°K for 90 min


SCIENCE

1.

27

Cellulose in Japan

MATsuzAKi

Figure 19. Relationship between centration and the degree of grafting vs. peroxide concentration in graft copolymerization of styrene onto cellulose triacetate preirradiated with gamma rays in air at 0°C. Grafting conditions, 60°C, 20 hr.

Table

IX.

Monomer R e a c t i v i t y Acrylate Cellulose

Trunk P o l y m e r

R a t i o s of Styrene w i t h

in the G r a f t

and C e l l u l o s e

Copolymer

n-Butyl

C o p o l y m e r i z a t i o n onto Triacetate r

at r

$ t

50°C.

BuA

r

St^ BuA r

grafted

1 38 ± 0 01

0 22 ± 0 01

6 3

nongrafted

0 90 ± 0 03

0 40 ± 0 01

2 3

Cel1ulose

grafted

1 16

0 01

0 42

±

0 01

2 8

t r i acetate

nongrafted

1 08 ± 0 01

0 54

±

0 01

2 0

0 .76 ± 0 01

0 38 ± 0 01

2 0

Cel1ulose

±

AIBN-initiated copolymer


28


SCIENCE

the adsorption of styrene or complex formation of styrene with radicals. (3)

Molecular Weight, Molecular Weight Distribution, and the Number of Grafted Polymers per Trunk Polymer. Since grafting reaction onto cellulose is usually carried out in heterogeneous phase, the termination is disturbed by the gel effect and the grafted polymer has higher molecular weight than the homopolymer. In homogeneous grafting onto cellulose derivatives dissolved in solvents, the molecular weight of the grafted polymer is not much different from that of the homopolymer. The molecular weight distribution of grafted polymers has been determined by several investigators. It was sometimes wide (46, £7) or i t had bimodal distribution(48). Our results(49) on the molecular weight distribution of polystyrene grafted onto cellulose triacetate showe the grafting the molecular weight distribution is similar to that of ordinary polystyrene. It is recognized that as the grafting proceeds, the molecular weight increases and the distribution becomes wider(Figure 20). As for the number of grafted chains per trunk polymer, Ikada et al.(50) showed that in the grafting reaction of styrene in methanol-water as solvent onto cellulose with simultaneous i r r a d i a t i o n , the number of branch molecules per trunk polymer is 0.915 after exhaustive extraction of unreacted cellulose and homopolystyrene. It is usually recognized that the number of grafted chains does not exceeds 1. New grafting methods which produce multi-branch grafted copolymers easily are expected to be developed. (4)

Stereoregularity of Polymers Formed in Graft Copolymerizat i o n . Since graft copolymerization onto s o l i d trunk polymers, especially onto f i b e r s , is a kind of organized polymerization in matrix, the structure of the polymers formed is expected to be different from those of the ordinary r a d i c a l - i n i t i a t e d polymers, because the s o l i d trunk polymers would give some influence on the molecular association and orientation of the monomers being polymerized. In our f i r s t report(51_), methyl methacrylate(MMA) and methac r y l i c acid were grafted onto various fibers such as nylon 6, cellulose triacetate fiber and polyester fiber with preirradiation techniques using gamma rays from a Co-60 source and the stereoregularity of the branch polymers isolated by acid hydrolysis was determined by proton NMR spectroscopy. The results i n d i cated that the stereoregularity of PMMA and poly(methacrylic acid) grafted onto viscose rayon and cotton was different from that of the polymers formed in ordinary radical polymerization. In the second report(52j, MMA was grafted onto viscose rayon, wood pulp, cellophane and p o l y v i n y l alcohol)(PVA). The stereoregularity of the polymers grafted onto rayon is different


1.

MATsuzAKi

Cellulose in Japan

29

from that of the polymers grafted onto wood pulp, mercerized wood pulp, cellophane and PVA films and powder. Recently, the stereoregularity of PMMA grafted onto various kinds of rayons, cotton 1 inters and mercerized cotton 1 inters was investigated in detail(53). The results shown in Table X i n d i cate that the stereoregularity of PMMA grafted onto ordinary v i s cose rayon filaments and staples and high tenacity viscose rayon staples of t i r e cord type is clearly different from that of the ordinary r a d i c a l - i n i t i a t e d polymers. Those rayons which give the different structures have high percentages of skin portion and the structure is different from that of polynosics and cuprammonium rayons. Therefore, i t is deduced that the polymerization in the skin structure affects the stereoregularity of polymers being polymerized. 5.

Application of Irradiatio

In the manufacturing of viscose rayons, aging of a l k a l i c e l lulose to lower the degree of polymerization of cellulose i s usually carried out. Imamura and Ueno(54) attempted to replace the aging of a l k a l i cellulose with i r r a d i a t i o n . Dissolving pulps were irradiated with gamma rays or electron beams in a range of 105 - 108 rad. The degree of polymerization and carbonyl and carboxyl contents after the irradiation depended on the total dose and not on the irradiation source. I r r a d i ation apparatus for large scale production of low DP pulps was investigated and among CO-60 gamma ray source, high voltage accelerator and low voltage accelerator, low voltage accelerator i s most suitable for industrial app1ication(55). Low DP pulps(DP 440) obtained by irradiation with gamma rays or electron beams were processed in viscose process without agi n g ^ ) . The analysis of the original and the irradiated pulps is shown in Table XI. The mechanical properties of rayon staples produced from the irradiated pulps are shown in Table XII. A l though they show tendency to have a l i t t l e low wet strength, wet elengation and knot strength, the difference is not appreciable. Pulps irradiated with electron beams showed the same results. 6.

Cellulose Industries in Japan

As for pulp and paper industries in Japan, Prof. Nakano w i l l write on the problems related to the industries. As for viscose process several companies already withdraw from the production and this tendency w i l l continue, because the increase of cost is expected due to the increase of prices of wood pulp and caustic soda, investment for pollution problems and the increase in labor wages. As a new product, Mitsubishi Rayon Co. i n s t a l l e d machines for production of viscose rayon spun bonds recently. The products are now being used for diaper l i n e n , l i n e r of paper table



39,5

7.1

H

I

4.1

4.1

6.3

36.6 39.2

Copper number

(%)

Number average DP

1.2

3.7

750

4.6

B-cellulose(%)

Original

92.0

Pentosan

G

5.3

5.3

36.6 37.6

58.1 57.1

H

A

X

G

4.4

H

4.2

3.8

1.8

3.7

3.7 1.9

3.6 1.2

465

7.9

4.9

8.3

776

87.5

I r r a d i ated

90.1

448

3.3

35.7 35.6

60.5 61.1

G

88.6

Original

Β

H

H

G

4.2

H

5.0

10.2

5.5

4.7 2.3

4.8 1.5

455

84.9 754

4.2

35.0

60.8

I r r a d i ated

4.9

37.2 32.5

57.9 62.5

G

88.2

Original

5.2

34.3 38.0

C

H

MERCERIZED ACID-HYDROCOTTON LYZED COTTON LINTER LINTER

61.5 56.8

COTTON LINTER

i r r a d i a t e d pulps

4.8

34.7 37.4

61.1 57.8

G

and gamma-ray

4.0

37.0 36.5

59.0 59.1

H

I r r a d i ated

A n a l y s i s of o r i g i n a l

5.5

36.7 39.9

G

59.3 54.5

H

t

HIGWENACITY RAYON STAPLE CUPRAMMONIUM RAYON (TIRE-CORD TYPE) (POLYNOSICS) FI LAMENT STAPLE

α-cellulose(%)

Pulps

G

ORDINARY VISCOSE RAYON STAPLE

STEREOREGULARITY OF P O L Y Î M E T H Y L METHACRYLATES) GRAFTED ONTO RAYONS AND COTTONS

59.2 54,6

H

T a b l e XI.

53,4

S

G

VISCOSE RAYON FI LAMENTS

T a b l e X.


Properties

(g/d)

Tenacity-/ Wet {%)

1 .64

17. 4

(%) U)

jDry

[Wet (g/d)' (g/d)

Knot tenacity

Loop Tenacity

1 .81

1 .53

20. 4

68. 5

[Dry/Wet (%)

2. 31

(g/d)

Tenacity/ Wet

3.37

1 .72

2.06

1 .75

1 .62

1.55

16.5

14.6

67.8

2.23

3.29

1 .75

2.05

1 .77

23.3

22.5

60.1

1 .73 18.3

(g/d)

Elongation

1 .67 2.88

18.0

62.0

1.81

2.92

/ Dry

(d)

(g/d)

Fineness

(g/d)

Knot tenacity

( % )

Loop tenacity

/Dry Elongation^.

^Dry/Wet {%)

(g/d)

/ Dry

(d)

1 .65

1 .56

15.6

15.5

67.5

2.24

3.32

1 .76

2.03

1 .80

22.0

18.1

58.9

1 .68

2.85

1 .68

1 .60

1 .55

15.7

13.8

65.5

2.04

3.10

1 .77

1 .92

1 .82

19.9

17.2

59.2

1 .64

2.77

1 .64

Pulp Β Conven No-aging -tional

and n o - a g i n g v i s c o s e

of rayon s t a p l e f i b e r s

Pulp A Conven No-aging -tional

by c o n v e n t i o n a l

Comparison of p r o p e r t i e s

Fineness

Table XII.

1 .77

1 .62

15.6

14.5

68.5

2.31

3.37

1 .74

2. 09

20. 6 1 .81

61 . 7 17. 5

1 .79

2.90

1 .64

1 .58

1 .53

14.9

14.6

64.2

2.03

3.16

1 .78

1 .95

1.72

19.7

17.3

56.4

1 .63

2.89

1 .64

Pulp C Conven -tional No-aging

processes.

obtained

32


0

2

4

6

SCIENCE

8

Molecular Weight (Μ) χ 10 Figure 20. Molecular weight distribution of grafted polystyrene formed in the copolymerization at 75°C

Ο G 20μ

260y

1 .1 m

fc

115 ml 8000 Fibers

Figure 21. Assembly of artificial kidney

•17 cm-


MATsuzAKi

Cellulose in Japan

STRAIN (%)

Figure 22. Stress-strain curves of hollow fibers

Cuprammonium

100

200

300

400 mmHg

MEAN TRANSMEMBRANE PRESSURE

Figure 23. Comparison of ultrafiltration rate


34


SCIENCE

napkins, and packaging f r u i t s . Cuprammonium process increased i t s production steadily and developed several new products, such as a r t i f i c i a l kidney and spun-bonded fabrics. Asahi Chemical Industry Co. and Asahi Medi cal Co. developed a r t i f i c i a l kidney made of hollow fibers of cu prammonium rayon. The assembly is i l l u s t r a t e d in Figure 21. It is made of 8000 hollow fibers(each ca. 300 deniers), of which i n side diameter is 260y. Cuprammonium rayon in Japan is manufac tured from cotton l i n t e r pulps. It has higher strength than re generated cellulose acetate hollow fibers as shown in Figure 22. It has higher rate of f i l t r a t i o n for water and urea, as shown in Figure 23. Especially, i t can be s t e r i l i z e d with ethylene oxide gas, permitting simple and short operations. Improved thrombogenicity permits less heparin dose and less residual blood after d i a l y s i s . Present production per month i s now 30,000 pieces. Asahi Medical Co. hollow cellulose acetate f i b e r s . They are used to prevent d i a l y sis of cancer c e l l s and/or b a c i l l u s , but pass proteins of low molecular weight. The system is c l i n i c a l l y tested for reinfusement of a s c i t i c f l u i d . Cellulose derivative industries are developing steadily. Methyl cellulose(D.S. 1.8-2.0) i s mainly used for cement mortar and s t a b i l i z i n g agent for suspension polymerization of vinyl chloride and vinylidene chloride. Other uses are cosmetic. Most of hydroxypropyl methyl cellulose is used in the f i e l d same as methyl c e l l u l o s e , but a low viscosity grade is used in tablet coating. Hydroxypropyl methyl cellulose phthalate(hydroxypropyl 6-10%, methyl 18-22%, phthalate 27-35%) is used for enteric coating and photo-sensitive polymers. This polymer i s superior to cellulose acetate phthalate since the l a t t e r has tendency to produce ace t i c acid during preservation. Literature Cited 1. Watanabe, S., Hayashi, J., and Imai, K., J . Polym. Sci. (1968) C, 23, 809. 2. Hayashi, J., Imai, K., Hamazaki, T.,and Watanabe, S., Nippon Kagaku Kaishi(1973) 1582. 3. Watanabe, S., Imai, Κ., and Hayashi, J., Kogyo Kagaku Zasshi (1971) 74, 1420. 4. Hayashi,J., Imai, K., and Watanabe, S., Memoires of the Facul ty of Engineering, Hokkaido University (1972) 65, 97. 5. Watanabe, S., and Hayashi, J., Kogyo Kagaku Zasshi (1970) 73, 1890. 6. Marrinan, H . , and Mann, J., J . Polym. Sci.(1956) 21, 301. 7. Hayashi, J., Sueoka, Α., Ohkita, J., and Watanabe, S., Nippon Kagaku Kaishi(1973) 146. 8. Hayashi, J., Sueoka, Α., and Watanabe, S., Nippon Kagaku Kaishi(1973) 153. 9. Watanabe, S., Imai, Κ., and Hayashi, J., Kogyo Kagaku Zasshi


1.

MATSuzAKi

Cellulose in Japan

35

(1971) 74, 1427. 10. Hayashi, J., Sueoka, Α., and Watanabe, S., Nippon Kagaku Kai shi(1973) 160. 11. Hayashi, J., Imai,K., Hamazaki, T., and Watanabe, S., Nippon Kagaku Kaishi(1973) 1587. 12. Hayashi, J., Yamada, T., and Watanabe, S., Sen-i Gakkaishi (1974) 30, 190. 13. Hayashi, J., and Yamada, T., Nippon Kagaku Kaishi(1975) 544. 14. Hayashi, J., 33rd Autumn Meeting, Chemical Society, Japan at Fukuoka(1975). 15. Fowler, J r . , W.F., Unruh, C.C., Mc Gee, P.Α., and Kenyon, W. 0., J. Am. Chem. Soc.(1947) 69, 1636. 16. Williams, H.D., U.S.P. 3,236,669(1966). 17. Meyer, K.H., Studer, Μ., and van der Wyk, A.J.Α., Monatshefte (1950) 81, 151. 18. Hata, K. and Yokota, Κ., Sen-i Gakkaishi(1966) 22, 96. (1968) 24, 415, 420. 19. Schweiger, R.G., Chem. & Ind.(1969) 10, 296. 20. Schweiger, R.G., Tappi(1974) 57, 86. 21. Nakao, O., Sen-i to Kogyo(1971) 4, 128. 22. Yamazaki, S., and Nakao, O., Sen-i Gakkaishi(1974) 30, T234. 23. Matsuzaki, Κ., and Miyata, T., Sen-i Gakkaishi(1966) 22, 173. 24. Matsuzaki, Κ., and Miyata,T., Kogyo Kagaku Zasshi(1967) 70, 770. 25. Miyata,T., and Matsuzaki, Κ., Kogyo Kagaku Zasshi(1967) 70, 2192. 26. Schwenker, J r . , R.F., Lifland, L . , and Pacsu, E . , Textile Res. J.(1962) 32, 797. 27. Schwenker, J r . , R.F., and Lifland, L . , Textile Res. J.(1963) 33, 107. 28. Sakamoto, Μ., Takeda, J., Ojima, N . , and Tonami, H . , J. Polym. S c i . , A-1(1970) 8, 2139. 29. Sakamoto, Μ., Choi, S.-C., Murakami, J., Sato, T., and Teshirogi, T., Sen-i Gakkaishi(1974) 30, Τ 286. 30. Sakamoto, Μ., Cho, H . , Yamada, Y . , and Tonami, H., Colourage Annual(1971) 90. 31. Sakamoto, Μ., Cho, H . , Yamada, Y . , Ojima, N . , and Tonami, Η., Sen-i Gakkaishi(1974) 30, Τ 17. 32. Tesoro, G.C., Sello, S.B., and Willard, J.J., J. Appl. Polym. Sci.(1968) 12, 683. 33. Matsuzaki, K., Nakamura, S., Go, C., and Miyata, T., Sen-i Gakkaishi(1968) 24, 235. 34. Matsuzaki, Κ., Nakamura, S., and Tsukamoto, Η., Sen-i Gakkai shi(1970) 26, 560. 35. Berlin, Α.Α., and Makarova, T.A., J. Gen. Chem. (USSR)(1963) 21, 1267. 36. Tonami, H . , Sen-i Gakkaishi(1958) 14, 100. 37. Yoshimura, S., Sen-i Gakkaishi(1965) 21, 317, 358, 410, 419, 479, 553, 560. 38. Arthur, J r . , J.C., Mares, T., and Hinojosa, O., Textile Res.


36


SCIENCE

J.(1966) 36, 630 and other papers. 39. Ogiwara, Y . , Hon, N-S., and Kubota, H . , J. Polym. S c i . , Polym. Chem. Ed.(1973) 11, 3243. 40. Ogiwara, Y . , Hon, N-S., and Kubota, H., J. Appl. Polym. Sci. 1974) 18, 2075. 41. Kubota, H . , Ogiwara, Y . , and Matsuzaki, K., J . Polym. Sci., Polym. Chem. Ed.(1974) 12, 2809. 42. Kubota, H., Ogiwara, Y . , and Matsuzaki, K., J. Appl. Polym. Sci.(1975) 19, 1291. 43. Matsuzaki, Κ., Nakamura, S., and Shindo, S., J . Appl. Polym. Sci.(1972) 16, 1337. 44. Sakurada, I . , Okada, T., Hatakeyama, S., and Kimura, F., J . Polym. Sci.(1964) C, No. 4, 1233. 45. Odian, G., Kruse, R.L., Kho, J.H.T., J. Polym. Sci. A-1(1971) 9, 91. 46. Huang, R.Y.M., and 7, 1393. 47. Huang, R.Y.M., and Chandramouli, P., J. Appl. Polym. Sci. (1968) 12, 2549. 48. Wellons, J.D., Schindler, Α., and Stannett, V . , Polymer(1964) 5, 499. 49. Matsuzaki, K., Komagata, H . , and Sobue, Η., Kogyo Kagaku Zasshi(1964) 67, 1949. 50. Ikada, Y . , Nishizaki, Y . , and Sakurada, I . , Bull. Inst. Chem. Research, Kyoto Univ.(1972) 50, 20. 51. Matsuzaki, K., Kanai, T., and Morita, N . , J. Appl. Polym. Sci. (1972) 16, 15. 52. Matsuzaki, Κ., and Kanai, T., J. Appl. Polym. Sci.(1976) 20, 2221. 53. Matsuzaki, Κ., and Kanai, T., unpublished results. 54. Imamura, R., Ueno, T., et al., Kamipa Gikyoshi(Japan Tappi) (1971) 25, 121, 242, 465, 512. (1972) 26, 164. 55. Makita, Μ., Sen-i Gakkaishi(1974) 30, Ρ 260.


2 The Relationships between Fibrous Materials and Paper Products. Concepts. Prospects CRISTOFOR I. SIMIONESCU Polytechnic Institute of Jassay, Romania

1. The concept o materials and paper processes of paper converting and obtainment. Paper characteristics For quite a long time, relations which can be established between pulp, as the original fibrous material, and paper, the end product of a series of intermediate technological processes, have been the intuitive concern of paper producers. Yet the detection of qualitative and especially quantitative relations apt to outline the reciprocal influences between the original properties of the cellulose fibrous material and those of the paper end product (physical, Theological, mechanical strength paper properties) is a matter of future achievement. In the course of paper-converting a series of operations and processes (which are sketched out in figure 1) come between pulp (the raw material) and paper (the end product). Modern technologies c a l l for an additional use of auxiliary (non-fibrous) materials having specific functions. The use of adhesives leads to a reevaluation of the above mentioned sketch of influences and thus we get a completed form (figure 2). From figure 2 we may infer that pulp is l i k e l y to be influenced by an addition of adhesives which, in their turn, exert an influence on the fundamental operations. However pulp has a decisive part in lending paper certain specific characteristics. Similar decisive actions are brought forth by a number of adhesives. 39 In Cellulose and Fiber Science Developments: A World View; Arthur, J.; ACS Symposium Series; American Chemical Society: Washington, DC, 1977.

40

CELLULOSE

FAC

PULP ^

Q_ _l

A

LL

Ζ

which determines the degree of s i z i n g , the r e t e n t i o n of the f i l l i n g m a t e r i a l , the dyeing capacity, the forming and dewatering of the sheet on the paper machine. The studies bear evidence ( 3 . 4 ) of a greater 5 p o t e n t i a l i n reed (-9 mV) and straw ( - 8 , 5 mV) pulp, as compared to bleached spruce f i r pulp (-6 m\0 . This explains the d i f f e r i n g behaviour during the paper s i z i n g process i n point of c o l l o i d a l i n s t a b i l i z a t i o n which takes longer i n reed and straw pulps than i n spruce f i s i z i n g observe the reed pulp

• > • •— Water NaOH Alcohol 10% ethylic

Table

5

53.53

47.03 28.77

22.37

Cellulose Lignin

8.25

17.11

Pentosans

1.86

2.1

Cellulose/ lignin ratio

%2 ~ beating degree of beech pulp, °SR

x^ - beech pulp, %

χ

- 0.00005 X o

2

χ

n

9

- O.OOOOlx + 0.00067 x x

g

+0.00043 χ χ + 0.00373 x

Opacity a f t e r calendering

χ

χ

y » 0.77 + 0.00151 χ

Tearing r e s i s t e n c e , g

2

χ

χ

Burst strength i n dry s t a t e , Kgf/cm

0

Regression equations ^ y = 4200 - 43 χ + 40 x y = 4.73 - 0.072 χ + 0.00017 χ y = 78.7 - 0.196 χ

Breaking length, m

Λ

c h a r a c t e r i s« +t4i c«s

C o r r e l a t i o n equations of strength p r o p e r t i e s of paper obtained with short f i b e r s pulp

0.34

%

Ash

Beech

Species

4

Chemical composition of beech and spruce

Table

2.

Fibrous Materials and Paper Products

SIMIONESCU

53

Figure 12. Variation of the waterproofing characteristics of the preconsolidated paper varie

0

25 50 75 100 BEECH PULP

Beating degree of the two pulps is 40° SR, with an addition of 3% colophony glue and 1% PPE resin.

0A80 (U60 £(K40 δ 0.420

60°SR 48°SR 40°SR 31°SR 20°SR 29 50 71 100 BEECH PULP [%]

£0.400 CL

g 0.380 ο 0.360

Figure 13. Variation of the compressi bility of preconsolidated papers vs. the variation of the bleached beech pulp addition and of the beating degree of softwood, with an addition of 3% colo phony glue 1% PPE resin, and 12.5% kaolin y

Figure 14. Variation of superficial con ductivity and zetha-potential vs. PPE con tent zetha-potential. (O) Unbeaten pulp, (Φ) beaten pulp; superficial conductivity (X) unbeaten pulp, (—) beaten pulp.


54

CELLULOSE AND-FIBER SCIENCE

£ 7000t

g 4000> x3000-

% PPE

Figure 15. Strength variation of dry papers obtained from (a) unbeaten and (b) beaten bleached softwood sulfate pulps, with an addition of PPE resin

2500 r 22502000•1750 r H1500E

§ i o o o -

* 750-

(/>

t

h 500fi

OLu-

Q5

1.0

2.0

%.PPE

3.0

Figure 16. Strength variation of wet papers obtained from (a) unbeaten and (b) beaten ground bleached softwood sulfate pulps with an addition of PPE resin


2.

siMiONESCu


55

1.0-

I 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 PPE,%

ο J

*0

Figure 17. Dimensional variation of two types of paper with the amount of added PPE resin. (1) Di mensional variation of type 1 under the influence of a 2% melamine addition; (2) dimensional varia tion of type 1 with the addition of PPE resin; (3) dimensional variation of type 2 under the influence of a 5% melamine addition; (4) size variation of type 2 with the addition of PPE resin.

2

\.,PPE

a

°

Figure 18. Suspension breaking length variation vs. the addition of PPE resin and consistence in bleached sulfate pulps from unbeaten softwood materials


CELLULOSE AND FIBER SCIENCE

56

A s i m i l a r v a r i a t i o n takes place i n dry and wet r e s i s t a n c e s and dimensional s t a b i l i t y as can be seen i n f i g u r e 19. The changes c i t e d above may be accounted f o f by the p e c u l i a r T h e o l o g i c a l behaviour of the f i b r o u s suspension i n the r e g i o n of the i s o e l e c t r i c point, which ensures optimum conditions f o r the paper f o r mation* Operations such as s i z i n g , short f i b r o u s materials r e t e n t i o n , f i l l i n g materials r e t e n t i o n and even dewatering on the paper-machine are also l a r g e l y i n fluenced by introducing PPE adhesive i n t o the paste(1S)« A maximum degree of s i z i n g i s achieved with an a d d i t i o n of only 1 percent aluminium sulphate i n case of the output i n usual processing. The papers thus obtained have a pH tending to the n e u t r a l value (6,5) and physical-mechanical p r o p e r t i e s s i m i l a r to those r e s u l t i n g from the c l a s s i c a l r e c e p t i o n (14* 2021). Figure 20 shows the described v a r i a t i o n s . As regards the recorded e f f e c t s upon f i l l i n g materials r e t e n t i o n and short f i b r e s r e t e n t i o n , they are to be found i n f i g u r e s 21 and 22. The study of vallum papers, processed i n the presence of the PPE adhesive, r e s u l t e d i n the f o l l o w ing c o r r e l a t i n g equations: F(%) = 0.5

3(mV) = 0.12

0.5 χ

+ 0.73 x

χ

0.03 χ 0.105

2 χ

- 0.442 x x 2

2

+ 1·383 χ

- 0.725 x

+ 0.116 x ^

2

- 1.25 x| - l . l x

+ 0.934 x

χ

χ

5

2 2

?

-

- 0.011 x

+ 0.262 x ^

(1)

5

2 ?

+

-

5

(2)

where the dependent v a r i a b l e s are: F - fibrous material retention y i e l d J - zetha e l e c t r o k i n e t i c p o t e n t i a l of the suspension The independent

v a r i a b l e s are the f o l l o w i n g :

x ^ colophony glue a d d i t i o n x - aluminium sulphate a d d i t i o n x*- PPE r e s i n a d d i t i o n 2


2.

siMiONEScu


57

ε

CL

3θηΙ—«-J ^ 0

1.0

J U

2.0

3.0 Ρ Ρ Ε , %

Figure 19. Suspension breaking length variation vs. the addition of PPE resin and consistence in bleached sulfate pulps from beaten softwood materials

100-

Figure 20. pH of the environment and the sizing degree of the papers obtained with 3% colophony glue with and/or with out an addition of 1% PPE resin and rising quantities of aluminum sulfate or natrium aluminate + aluminum sulfate. Degree of sizing: (O) 5% aluminum sulfate; (Φ) 1% PPE + 1% Al (SO ) ; ((D) 1% PPE + 1% aluminum sulfate + natrium aluminate. pH: (X) 5% aluminum sulfate; (-{-) 1% PPE + I % aluminum sulfate. 2

%Al2(SO^) .18H 0 3

2

k s


58


Figure 21. Retention yield variation of the calcium carbonate with bleached sulfate pulp which has been beaten for 35 min with an initial addition of 1-10% fillings; 2-20% fill ings; 3-5% fillings

6Θ-

%,PPE

Figure 22. Variation of the titanium dioxide with PPE resin addition retention yield, in the case of bleached sulfate softwood pulp which has been beaten for 35 min in a Jokro mill, with an initial addition of 1-20%fillings;2-10%fillings;3-5% fillings


2.

siMiONESCu


59

The l a s t values have the f o l l o w i n g l i m i t s : s

x^ = 0-3 percent; x 0 - 8 percent; x^=0-1.2 percent 2

In the s p e c i f i c case when i n equation (1) we use 3 percent colophony glue ( x = +1.682) and 4 percent of aluminium sulphate (x - 0 ) , we obtain equation (3): 1

0

d

F » 95.84 + 0.73 x

- 1.1 x

?

2

(3)

The r e l a t i o n describes a curve having a maximum when F = 95.97 percent, corresponding to a quantity of 0.718 percent PPE r e s i n (x^ = +0.332). The y i e l d increas r e t e n t i o n i s F = 9.1 percent. Under s i m i l a r c o n d i t i o n s , we get equation

3

(4)

2

-0.23 + 1.82 x - 0.011 x (4) where from we f i n d the f o l l o w i n g value J = +0.37 mV, f o r which the y i e l d i s at i t s highest (region o f the isoelectric point). S i m i l a r l y i n f l u e n c i n g f a c t o r s of the PPE a d d i t i o n i n the stock dewatering process on the newspapermachine have been determined. The f o l l o w i n g c o r r e l a t ing equations have been used: s

3

?

1

Κ (cm s*" ) = 9.1 - 1.18 χ - 0.42 χ

2

- 0.32 x

χ

1

(Hcrn^ )

2

+ 0.322 x

χ

- 0.294 x ^

2

= 2.87 + 0.273 χ

χ

- 0.1 x + 0.04 x-j + 0.05 x + 0.0146 XjXg 5

- 0.203 χ - 0.43 x

2 χ

2 3

- 0.763 x

2 2

- 0.092 x ^

2 3

+ 2.28

2

(5)

+ 0.0167 x

2

J (mV) = 1.18 + 0.885 x

-

?

-

2

+ (6) -

- 0.763 x

2

-

2

- 0.705 χ χ 2

?

(7)

As dependent v a r i a b l e s the f o l l o w i n g have been assumed: Κ - f i l t e r i n g rate / (> 'c ΟC Ε %

73

determining influences

PAPER

determining influences

Figure 23. Diagram tives-paper product interrelations

Figure 24


SCIENCE

2.

siMiONEScu


69

The diagram provides the p o s s i b i l i t y of systematica l l y exploring the interferences of the three i n fluencing factors. The concern with using mixtures of chemical and pulp f i b r e s o r i g i n a t e d f i r s t l y i n the l i m i t e d performances of t r a d i t i o n a l paper i n some of i t s uses and secondly i n the high cost of synthetic paper obtained from chemical f i b r e s 100 percent* A compet i t i v e evolution of the two types may be foreseen. Economical reasons and improvement of e x i s t i n g technologies w i l l exert a great influence on t h i s evolution. Conclusions The i n t e r r e l a t i o n product have been c o n s i s t e n t l y c h a r a c t e r i z e d . The leading general concept asserts the i n t e r ference of moderate influences or of determining actions r e s u l t i n g from the fundamental operations and the a d d i t i o n of a d d i t i v e s , between the properties of the i n i t i a l f i b r o u s material and those of the f i n a l paper product. The i n v e s t i g a t i o n has been d i r e c t e d towards the f i b r o u s material-additives-fundamental operations-paper c h a r a c t e r i s t i c s system i n the case of short f i b r e s from annual plants pulp (reed, straw) and hardwoods. Q u a l i t a t i v e c o r r e l a t i o n s has been determined i n the f i r s t place and afterwards quantit a t i v e i n t e r p r e t a t i o n has been given to them. Some r e l a t i o n s proved apt f o r being introduced into a mathematic model, the i n f l u e n c i n g f a c t o r s enabling the optimization of paper c h a r a c t e r i s t i c s or of the fundamental operations. The determining influence of a d d i t i v e s has been i l l u s t r a t e d by use of the c a t i o n - a c t i v e PPE r e s i n . The r e s i n modifies e s s e n t i a l l y some fundamental operations and has a d i r e c t e f f e c t on improving paper properties. S i m i l a r i n t e r r e l a t i o n s have been determined i n the case of a r t i f i c i a l and synthetic polymers introduce ced i n the composition of the pulp f i b r o u s m a t e r i a l . The e f f e c t s are due to the symbiosis between the properties of the paper properties of the synthetic polymers and of the n a t u r a l pulp.


70

CELLULOSE AND FIBER SCIENCE Literature

1 Cr. Simionescu, Gh. Rozmarin, Chimia stufului, Ed. Tehnică, Bucureşti, 1966. 2 Cr. Simionescu et all, Zellstoff und Papier, 1963, 12, 327. 3 E. Poppel, S. Petrovan, Cr. Simionescu, Buletinul Inst. politehnic Iaşi, 10 (14), 1-2, 155 (1964). 4 Cr. Simionescu, Gh. Rozmarin, Chimia lemnului şi a celulozei, v o l . I , Litografia I . P . I a ş i , 1972. 5 V. Diaconescu, E. I.P. I a ş i , 9(13), 3-4, 155 (1963). 6 V. Diaconescu, E . Poppel, P. Obrocea, Celluloză

şi Hîrtie, 12, 5-6, 184(1963). 7 Cr. Simionescu, M. G r i g o r a ş , A. Cernătescu-Asandei Chimia lemnului din RPR, Ed. Academiei R.P.R., Bucureşti, 1964. 8 E . Poppel, S. Petrovan, Contract de cercetare ştiinţifică (Combinatul de C e l u l o z ă şi Hîrtie Drobeta Turnu-Severin), 1974. 9 Ε. Poppel, S. Petrovan, Das Papier, under press. 10 E. Poppel, S. Petrovan, Contract de cercetare ştiinţifică (Combinatul de C e l u l o z ă şi Hîrtie Drobeta Turnu-Severin), 1975. 11 Cr. Simionescu, E . Poppel, S. Petrovan, Paper presented at the International Meeting of the International Academy of Wood Science, Banska Bystrica, 1975. 12 13 14

E . Poppel, S. Petrovan, Cr. Simionescu, Chem. and Technol. 2, 4, 444 (1968).

Cellulose

E. Poppel, I . Bicu, Das Papier, 2 2 , 12, 882(1968). E . Poppel, I . Bicu, Das Papier, 23, 10 A, 672(1969)

15

E . Poppel, I . Bicu, Das Papier, 26, 4, 162 (1972).


2.SIMIONESCUFibrous Materials ajid Paper Products

71

16 I . Bicu, V. Popa, E. Poppel, Cr. Simionescu, Z e l l stoff und Papier, 2 1 , 1,8 (1972). 17 18

E. Poppel, I. Bicu, V. Dobronăuţeanu, Das Papier, 29, 3,93 (1975). E. Poppel, I . Bicu, Z. Ládo, Cellulose Chem. and Technol., 9, 4, 413 (1975).

19 20 21 22

I. Bicu, V. Popa, E . Poppel, C e l u l o z ă şi H î r t i e , 18, 10, 498 (1969). Ε. Poppel, Cr. Simionescu, Buletinul I.P. Iaşi, 8 (12), 1-2, 1977 (1962) I. Bicu, Doctora

ş

E. Poppel, D. Ciobanu, Zellstoff u. Papier, 1975, 3, 68. 23 24 25 26

E. Poppel, D. Ciobanu, Zellstoff u. Papier, 1975, 5, 135. E. Poppel, D. Ciobanu, F. Andruchovici, Zellstoff u. Papier, 1975, 11, 323. E. Poppel, D. Ciobanu, Zellstoff u. Papier, under press. Cr. Simionescu, A. Liga, Patent R.S.R. 73064(1972)

27 28

N. Asandei, A. Liga, C. Stan, C. Moisă, Patent R.S.R. 59353 (1976). Cr. Simionescu, V. Rusan, A. Liga, V. Nuţă, D. Buhman, unpublished data.

29

D. Feldman, M. Ciubotaru, M. Ciugureanu, Rev. Roum. de Chimie, 1976 (under print) 30

A. Stoleriu, paper communicated at the first Microsymposium of macromolecular chemistry, I a ş i ,

November 14-15, 1975. 31

D. Buhman, Z. Ládo, V. Ungureanu, paper communicat ed at the 1st Microsymp.macromo.chem.Iaşi,14-15.XI. 1975.


3 History and Future Trend of Synthetic Paper Technology in Japan SHOZO IMOTO Toppan Printing Co., Ltd., 5,1-Chome Taito, Taito-ku, Tokyo, Japan

The brief history of Synthetic Paper or Plastic Paper in Japan i s summarized as f o l l o w s : (1) U n t i l the year o f 1967 when Foamed P o l y s t y r e n e or Polyethylene Sheet was developed, (2) U n t i l the year o f 1970 when the idea o f Raw M a t e r i a l Revolution, so to speak, c e n t r a l i z i n g the u t i l i z a t i o n o f P l a s t i c Paper or S y n t h e t i c Paper with P l a s t i c F i l m Base, was embodied i n the form of i n d u s t r i a l i z a t i o n . (3) U n t i l .the year o f 1975 when White P l a s t i c Sheet f o r Vacuum Molding, i n p a r t i c u l a r , r e s u l t i n g from a mixture o f M i n e r a l F i l l e r i n l a r g e q u a n t i t i e s and S y n t h e t i c Pulp, as w e l l , was i n d u s t r i a l i z e d . With the above d i v i s i o n a l periods i n mind, f i r s t o f a l l , I would l i k e to describe the trend mainly from the t e c h n o l o g i c a l point o f view: L a s t l y , I would l i k e to introduce the newest type o f S y n t h e t i c Paper on which we are a t present doing research, attempting to sound the t e c h n o l o g i c a l trend i n the f u t u r e . (1) Foamed Sheet Age (Up to 1967) In the wake o f Wood Pulp Paper d i d the second paper, v i z . , Non-Woven F a b r i c s come out. The t h i r d paper was none other than Foamed P o l y s t y r e n e Sheet that made i t s debut i n i 9 6 0 . None-Woven F a b r i c s are mostly used i n s t e a d o f c l o t h , while Foamed P o l y s t y r e n e Sheet could be used i n the main f o r lunch boxes and other sundry items a f t e r vacuum molding, being seldom made use o f as a s u b s t i t u t e f o r paper. As regards Foamed P o l y s t y r e n e Sheet, s e v e r a l Japanese manuf a c t u r e r s such as SEKISUI KAGAKU CO. and K0KUSAI PULP CO. became capable o f producing 500 t . - 1,000 t . per year r e s p e c t i v e l y i n or about the year o f i 9 6 0 . T h i s Sheet was aimed a t being developed enough to r e p l a c e paper i n uses due p a r t i a l l y to i t s p e a r l - l i k e b e a u t i f u l g l o s s y

72


3.

iMOTO

73

Synthetic Paper Technology in Japan

surface and p a r t i a l l y to i t s p a p e r - l i k e r i g i d i t y and opaqueness characteristically. Above a l l , SEKISUI had e s t a b l i s h e d i t s plant i n the u n i t e d States,too, r e i n f o r c i n g i t s o p e r a t i o n t h e r e . Nevertheless, i t proved to be i n s u f f i c i e n t as paper i n p o i n t o f s t r e n g t h , p r i n t a b i l i t y , e t c . , with the r e s u l t that i t s s a l e s amount was not as s a t i s f a c t o r y as had been a n t i c i p a t e d . I t was not u n t i l the year o f i960 that NIPPON ART PAPER CO.R. & D. D i v i s i o n , present JAPAN SYNTHETIC PAPER CO., improved the stength and p r i n t a b i l i t y o f t h i s Foamed Polystyrene Sheet under the brand o f "Q-Foam" o f Foamed Polyethylene Sheet. Subsequently, from 1965 through 1971 t h i s improved type o f Foamed Polyethylene Sheet had been produced and o f f e r e d f o r s a l e by JAPAN SYNTHETIC PAPER CO. Then, MITSUI POLYCHEMICAL CO.'s wholly-owned s u b s i d i a r y HI-SHEET KOGYO CO took th produc t i o n , producing 3*000 t connection, i t s p h y s i c a p r o p e r t i e represente y TABLE ( 1 ) . (2) F i l m Base Type S y n t h e t i c Paper Age(from 1967 t o 1970) I t was i n 1966 that JAPAN SYNTHTIC PAPER CO. announced another brand, "Q-Per", a type o f S y n t h e t i c Paper with o n l y i t s s u r f a c e paperized by c h e m i c a l l y t r e a t i n g by means o f the same f i l m as the S y n t h e t i c Paper with the brand o f " Q - K o t e " , f i n a l l y became the cynosure o f a l l eyes not o n l y i n Japan but a l s o a l l over the world what with i t s p r i n t a b i l i t y and p r i n t i n g e f f e c t estimated a t the highest q u a l i t y as p r i n t i n g paper. I f the cost o f the b i a x i a l l y o r i e n t e d -film could reach a t 60 cents per kg. through the mass-production o f 1,000 ton per month and the new t e n t e r i n g technology being under developing by Dr. Shoei Yazawa o r Mitsubishi-Monsanto Chemical Co., the S y n t h e t i c Paper Q-Kote s p r i c e would be estimated approximately 1.5 times as much as the high q u a l i t y coated paper. On the occasion o f t h i s t e c h n o l o g i c a l development, the Japanese Science and Technology Agency i n the Japanese Government was s t r o n g l y convinced that S y n t h e t i c Paper would f i l l i n the shortage o f pulp f o r paper i n Japan and c o n t r i b u t e to development of Japan's Petrochemical Industry, too. As a Government p o l i c y , they t h e r e f o r e decided to promote t h i s i n d u s t r y . Encouraged by t h i s Government p o l i c y , on the other hand, JAPAN SYNTHETIC PAPER CO. completed i t s production f a c i l i t i e s f o r Q-KoteQ and "Q-Per" capable o f producing 3*000 t . per year i n 1969 as i t s 1st term program. Afterward, OJI-YUKA SYNTHETIC PAPER CO. with the brand o f "UPO-EF" and SEKISUI KAGAKU CO. with the brand o f " P r i n t e l " r e s p e c t i v e l y set up t h e i r production f a c i l i t i e s f o r t h e i r products i n I 9 7 L In t h i s regard, "Q-Kote", "Q-Per", "UPO-EF", and " P r i n t e l a r e as represented i n performance by TABLE(1). Furthermore, p r a c t i c a l i t y o f t h i s type o f S y n t h e t i c Paper was promoted. To c i t e a few examples, books made o n l y from f,

flt

ff

1 1

11


74

CELLULOSE

A N DFIBER

SCIENCE

"Q-Kote" and "Q-Per" were published, and some pages o f a c e r t a i n l e a d i n g weekly with i t s weekly c i r c u l a t i o n o f 1,000,000 copies were composed o f t h i s type o f S y n t h e t i c Paper t o say nothing o f Posters, Pamphlets and W r i t i n g Paper. In a d d i t i o n t o the above three(3) manufacturers n e a r l y ten (10) others announced F i l m Base Type S y n t h e t i c Paper along with t h e i r samples. Meanwhile, UCC, MEAD CORP.(U.S.A.) and XYLONITE CO.(U.K.) had been developing Pigmented F i l m Type S y n t h e t i c Paper. F o r example, the performace o f MEAD CORP. s "Aero-Art" i s as represented by TABLE ( 1 ) . Simultaneously i n Japan such manufacturers as CHISSO CO. and NITTO-BOSEKI CO. had been making researches on S y n t h e t i c F i b e r o r Pulp f o r paper, though they could not i n d u s t r i a l i z e this material. (3) S y n t h e t i c Pul Age (1971 - 1975) 1. Slump i n F i l m Base Type Demand Development o f demand f o r S y n t h e t i c Paper as replacement o f conventional paper has turned out to be extremely d i f f i c u l t owing to Japan's economic r e c e s s i o n on the whole, deep business depression adversely a f f e c t i n g the high c l a s s paper i n d u s t r y i n p a r t i c u l a r , the " D o l l a r Shock", r a i s e s i n petrochemical m a t e r i a l s caused by boosts i n o i l , e t c . The a f o r e s a i d preceding three(3) manufacturers have e x t e r t e d every e f f o r t to commercialize t h e i r products, i n the hope that the products could be a p p l i e d to users even a t high p r i c e s , suf£ f e r i n g from t h e i r r e s p e c t i v e low o p e r a t i o n . However, i n my personal estimation, t h e i r r e s p e c t i v e product i o n i n the year o f 197^ i s as represented by TABLE (2) 2. Debut o f S y n t h e t i c Pulp MITSUI-ZELLERBACH CO.(JAPAN), a J o i n t Venture f i r m e s t a b l i s h e d by CROWN-ZELLERBACH CO.(U.S.A.) and MITSUI PETROCHEMICAL CO. b u i l t a plant capable o f producing 500 t . per month o f S y n t h e t i c Pulp under the brand o f "SWP"(Synthetic Wood Pulp) i n 1973, throwing l i g h t on the S y n t h e t i c Pulp Age. According t o the manufacturing method o f S y n t h e t i c Pulp that had been p r a c t i c e d u n t i l then, i n the f i r s t place, p l a s t i c P o l y mer was produced, and i t was converted i n t o f i b e r or pulp, though. "SWP" was prepared by a new process, s u b j e c t i n g Monomer t o Polymerization and converting i t i n t o f i b e r simultaneously. T h i s S y n t h e t i c Pulp was the f r u i t o f exceedingly epochal t e c h n o l o g i c a l development, resembling Wood Pulp a great deal i n both shape and q u a l i t y . For some uses i t cou;d blend with Wood Pulp and be formed p r o p e r l y by the conventional paper machine. "SWP" only could be subject t o paper-forming, however. As compared with conventional paper made from Woof Pulp only, t h i s mixture could be c h a r a c t e r i s t i c i n performance o f High Opaci t y and Brightness, L i g h t e r Weight, Higher Clearness, Dimension 1


3.

ΐΜΟτο

Synthetic Paper Technology in Japan

75

S t a b i l i t y against Humidity, Heat S e a l a b i l i t y and Emobossability. On top of these p r o p e r t i e s , i t i s e x c e l l e n t i n dehydration and evaporation. In c o n c l u s i o n , a d d i t i o n of S y n t h e t i c Pulp i s s a i d to enlarge the Machine Speed. Subsequent to MITSUI-ZELLERBACH CO.'s development, HITACHI KASEI CO., TORAY CO., e t c . s t a r t e d developing S y n t h e t i c Pulp. In consequence, the e n t i r e production of S y n t h e t i c Pulp i s estimated to exceed that of F i l m Type S y n t h e t i c Paper, as represented by TABLE (2)during the p e r i o d of 1975 and 1976. 3· H i g h l y Pigmented F i l m Type In view of the f a c t that the cost of Petrochemical Resin skyrocketed, causing a boost i n the p r i c e of the product, and that the combustion furnace i s apt to be damaged due to high c a l o r i e when i t be burned, s e v e r a l manufacturers have promptly s t a r t e d to develop H i g h l Pigmented F i l Shee c o n t a i n i n more than 60% of low-price lower combustion c a l o r i e , 1971· larges , LION YUSHI CO. has begun to turn out the above i n i t s production c a p a c i t y of 10,000 t . per year. I t s product under the brand of "Kalp" i s as represented i n performance by TABLE ( 1 ) . Sulphur emanates from Crude Petroleum when i t burns. T h i s sulphur could be converted i n t o Gypsum, which could be made i n sheetings by means of P o l y o l e f i n Resin as Binder i n a s k i l l f u l , but simple way. Crude Petroleum imported i n t o Japan contains l o t s of S u l f u r , and t h e r e f o r e i t would be f o r c i b l y changed to CaS04 i n order to prevent a i r p o l l u t i o n , just a f t e r combustion. A n d , P in l a r g e q u a n t i t i e s could be s u p p l i e d to us at a low cost, as i3ie good f i l l e r . Probably because of imcomplete engineering i n the field of P a p e r i z a t i o n only t h i c k sheet f o r Vacuum Molding has so f a r been put on the market here i n Japan, though, I t i s expected that P a p e r - l i k e F i l m would be produced i n the near future. Aside from the above, P o l y o l e f i m Sheet f o r Vacuum Molding c o n t a i n i n g over 60% of such Iorganic F i l l e r as Ca C03 and CaS04 i s at present manufactured by four(4) Japanese makers. I t s d e n s i t y i s 1.4 - 1.6, i t s combustion c a l o r i e , 3»000 - 4,000 Kcal/kg«i i t s thickness, 0.5 - 1mm. and i t i s noteworthy that i t could he deeply molded i n almost the same as C l e a r Resin. Such improvement of High F i l l e r P l a s t i c Sheet, to the best of my knowledge, could be a s c r i b e d not merely to progress i n Technology on Treatment of Inorganic M a t e r i a l but to betterment of Engineering i n Mixing and Sheeting, yoo. 4. Prospects. 1. I t i s expected that S y n t h e t i c Pulp w i l l be popular with users at l a r g e . / d ^ In case of recovery of Scrapped Paper, or Spoilage, on the con^ion that some per cent of S y n t h e t i c Pulp i n v o l v e d i n i t , should prove not to i n t e r f e r e , u t i l i z a t i o n of S y n t h e t i c Paper G v

s u m


76


Tabled)Properties and Printability of each Synthetic Paper Type Type Physical properties Item Thickness, μ Density, tin? Whiteness, 7.

Opicity. % Gloss.

front. %

Test method JI5P-8124 JISf*81l8 JISP-8I18 JISP-8123 JISP-8138 JISP-8142

(«fr~-6Vo back. %

•

Smoothness, front, m m t y back, m m r * Tensile strength MP, Ιφ6τί JISP-8113 Elongation MD. % JISP-8132 CD,% * Tming strength MD, ^ JIS P-8M6 CD.* • Ink lusterdndifo), ·/. JIS P-8K2 Ink depositing — Ink absorption — Ink Transfer Ink setting time. m i n . —

-

wfocepdperiaq Co* paperizjnj PR IN TEL Q-FOAM

(bmjwRUive tests HiSulfite production Production of fodder yeast from sulfite s p e n t liquor Production of furfural a s dissolving kraft pulp by products First production of hardwood kraft liner in the w o r l d Production of l i g n i n rubber Production of polystyrene f o a m paper P r o d u c t i o n of refiner groundwood Construction of chip exclusive c a r r i e r Pulp wood: Hardwood>Softwood First productio world Production of x y l o s e a s dissolving kraft pulp by-products Table 7 Consumed pulpwood statistics (1,000 m ) 3

Year 1960 62 64 66 68 70 72 73 74 75

Softwood 7.861 7.674 7.894 8.132 9.348 12.018 13,550 15.131 15.912 14,096

Hardwood 4,481 6,516 8.538 10,352 12.698 16.325 17.258 17.783 17.163 14.553

Total 12.342 14.190 16.432 18.482 22.046 28.343 30.808 32.914 33.075 28,649

Table 8 Supplied p u l p w o o d statistics(1,000m ) 3

Year 1960 65 67 68 70 72 73 74 75

Domestic Roundwood Chip 7,983 7,673 9.975 7,401 6,566 4,419 3,712 3,799 2,672

3.040 8.479 10,005 11.950 16.050 17.966 17,446 17,716 14,324

Imports Roundwood 193 207 163 299 559 370 667 1,232 578

Chip

—

254 1,401 2.927 4.726 7.159 10.556 12.820 11,213

Total 11.216 16.613 21,544 22.577 27,901 29.914 32.381 35,627 28,787


SCIENCE

NAKANO

Japanese Pulp and Paper Industry

177

Table 9 Imported p u l p w o o d statistics(1,000m ) 3

Year

North America

—

1960 65 67 68 70 72 73 74 75

253 U02 2,909 4,091 5.435 7,501 8.729 7,533

Soviet Union 193 167 97 55 257 128 417 579 723

O c e a n i a Others

— — —

— 41

65 3 259 779 158 854 1,112 2,349 956 4.744 3,535

Total 193 461 1.564 3,226 5.285 7,529 11,223 14.052 11,791

TablelO W o o d s p e c i e s a s p u l p w o o d Wood s p e c i e s Softwood

Domestic w o o d

Hardwood

8.

Foreign wood Soviet U S.A. Southern a r e a Domestic w o o d

pine. fir. s p r u c e , hemlock. sugi(Cryptomeria), cypress, l a r c h , hiba(Thujopsis) spruce, fir, Scotch pine, larch Douglas f i r, hemlock. white fir, spruce, cedar merkusii p i n e , r a d i a t a pine b e e c h , birch, alder, oak,tabu(Machilus), shii(Shiia)

Foreign w o o d Soviet Southern area

white birch, e l m , a s p e n , a s h mangrove, eucalyptus, lauan, gum(waste wood)

Table 11 Outlook of supply a n d d e m a n d of pulp a n d p a p e r ( U n i t : 1,0001) Items Pulp Demand Production Capacity Rate of operation,% Paper Demand Production Capacity Rate of operation^

1973

1974

11.475 10,781 1Q200 9.558 11.461 11.868 89.0

80.5

16.954 14.246 ]6J§2& 14.433 16,498 17,935 100.8

80.5

1975

1976

1977

1978

10,445 9.395 12,472

10.661 9.311 12.460

11.131 9.581 12,779

13,448 10.848

75.2

74.7

14,564 14.100 19.967

15.523 15,337 20.058

70.6

76.5

75.0

— —

16,227 20.752 16 7QQ 20.468 20.740 f

80.5

— —


178

CELLULOSE

a l o n g range view o f p u l p raw

AND

FIBER

SCIENCE

materials.

Resource developments i n o t h e r c o u n t r i e s Table 12 summarizes the r e s o u r c e development i n o t h e r c o u n t r i e s . At p r e s e n t , Japan i s p u r s u i n g a p a t t e r n which w i l l c o n t r i b u t e more t o the p r o s p e r i t y o f the h o s t c o u n t r i e s , i n o t h e r words, the i n d u s t r y i s t r y i n g t o go i n t o t i e - u p s w i t h the h o s t c o u n t r i e s t o undertake p l a n t a t i o n and even p u l p and paper p r o d u c t i o n i n t h e s e c o u n t r i e s . One o f the s u c c e s s f u l c a s e s o f the economic c o o p e r a t i o n i n the manner mentioned above i s the p r o j e c t i n B r a z i l . Waste paper T a b l e 13 shows the o r i g i n o f waste paper i n Japan. The share o f waste paper was i n 37~ 4 1 % o f paper and paperboard p r o d u c t i o fro 1969 t 1974. The i n d u s t r waste paper as p u l p raw m a t e r i a l . F o r t h i s purpose, The C e n t e r f o r the P r o m o t i o n o f the Use o f Waste Paper has been e s t a b l i s h e d t o f a c i l i t a t e the c o n s t a n t s u p p l y of waste paper and t o i n c r e a s e the share o f waste paper. The c h r o n i c i n s u f f i c i e n c y o f the waste paper r e c o v e r y system i n Japan has l o n g p r e v e n t e d the i n c r e a se of r e c o v e r y r a t e . At p r e s e n t , the i n d u s t r y w i s h e s to i n c r e a s e the share of waste paper used as raw mater i a l t o 45% by 1 9 8 5 . Non-woody p l a n t f i b e r The use of r i c e straw as raw m a t e r i a l was e a r l i e r t h a n t h a t of wood, t h a t i s i n 1878. The i n c l i n a t i o n o f c o l l e c t i o n season, the i n convenience o f c o l l e c t i o n , t r a n s p o r t a t i o n and s t o r a g e , low p u l p y i e l d and so on have p r e v e n t e d the i n c r e a s e o f straw p u l p p r o d u c t i o n . R e c e n t l y , a l l straw p u l p m i l l s stopped the p r o d u c t i o n o f i t i n Japan, because the e f f u i e n t problems was f u r t h e r t a k e n p a r t . However, from a p o i n t of f u t u r e s h o r t a g e o f p u l p raw m a t e r i a l , r i c e s t r a w s h o u l d be used a g a i n . I n the case o f r i c e s t r a w p u l p p r o d u c t i o n , a new p u l p i n g way must be found out, because the ash c o n t e n t o f r i c e s t r a w (about 17%) i s more t h a n t h a t o f wheat s t r a w (about 8%). Also, new s t r a w p u l p m i l l would be b e t t e r t o o p e r a t e i n s m a l l p r o d u c t i o n c a p a c i t y from a p o i n t o f the p o s s i b i l i t y o f easy c o l l e c t i o n . I n Japan, we can e s t i m a t e 1 2 , 0 0 0 , 0 0 0 t / y e a r of r i c e straw. Supposing t h a t the i n d u s t r y w i l l use 3 , 0 0 0 , 0 0 0 t / y e a r of r i c e straw and p u l p y i e l d i s 40%, about 1 , 2 0 0 , 0 0 0 t / y e a r o f s t r a w p u l p a r e t o be produced. C o n c e r n i n g p u l p p r o d u c t i o n from non-woody p l a n t , one company i s now making the p l a n t a t i o n o f some h e r b s , s o - c a l l e d pulp grass.


8.

NAKANO


179

P o l l u t i o n problems The p u l p and paper i n d u s t r y must meet t h e r e g u l a t i o n o f a n t i - p o l l u t i o n s e t by t h e government and t h e l o c a l a u t h o r i t i e s , a l t h o u g h t h e government has p e r m i t ted a t r a n s i t i t i o n a l p e r i o d d u r i n g which the i n d u s t r y can improve t h e p r o d u c t i o n system t o meet t h e e n v i r o n mental standards. The i n d u s t r y was r e q u e s t e d t o a c h i e v e BOD and COD 1 20 ppm and SS 150 ppm by June i n 1976. The s t a n d a r d s s e t by t h e l o c a l a u t h o r i t i e s a r e even more s t r i c t . A new paper m i l l e s t a b l i s h e d i n 1974 has agreed upon 12 ppm o f BOD w i t h t h e l o c a l a u t h orities. T h i s m i l l has been a d o p t i n g t h e c o a g u l a t i o n and a c t i v e carbon t r e a t m e n t s o f e f f l u e n t s . P o l l u t i o n abatement i n e x i s t i n g p u l p and paper m i l l s The e x i s t i n the closed' system o as a commonsence, p o l l u t a n t s s h o u l d be t a k e n i n t h e production processes. I t i s a l s o c o n s i d e r e d i n what p r o c e s s t h e s u r p l u s m a t e r i a l s s h o u l d be d i s c h a r g e d . Decrease o f w a t e r consumption I t i s well-known t h a t p u l p and paper m i l l s a r e s t r u g g l i n g t o save t h e w a t e r consumption. T h i s i s a c h i e v e d by i n c r e a s i n g the use o f r e c o v e r e d water and r e c y c l i n g w a t e r . There i s a n o n - e f f l u e n t paper board m i l l w h i c h i s u s i n g waste paper, a l t h o u g h t h e w a t e r consumption i s a c t u a l l y 2 - 3 ^/t paperboard. T h i s m i l l announced t h a t t h e i n c r e a s e o f o p e r a t i o n temperature cused by none f f l u e n t s o p e r a t i o n has p r e v e n t e d t h e s l i m e t r o u b l e . The m a t e r i a l y i e l d was about 90% s e v e r a l y e a r s ago, but a t p r e s e n t i n c r e a s e d t o 9 6 ~ 9 7 % * a f t e r t h e improvement o f the p r o c e s s e s . That i s , t h e p r e v i o u s p o l l u t a n t s was t o be t a k e n i n t h e p r o d u c t s , and t h e r e i s no d i f f e r e n c e from t h e former q u a l i t i e s o f paperboard. Although people says t h a t t h i s i s p o s s i b l e o n l y i n a paperboard m i l l , t h e r e may be a few p r o c e s s e s w h i c h c o u l d be a p p l i e d i n t h e p r o d u c t i o n o f c o n v e n t i o n paper. Development o f p o l l u t i o n f r e e p u l p i n g There a r e two p r o c e s s e s w h i c h have been p r o g r e s s e d by t h e use o f p i l o t p l a n t ; PFP p r o c e s s by Japan P u l p and Paper I n s t i t u t e and HOPES p r o c e s s by Toyo P u l p Company. Both p r o c e s s e s have been f i n a n c e d by s u b s i d y o f t h e Government. Another p u l p i n g p r o c e s s , s o - c a l l e d a l k a l i methanol p u l p i n g has been s t u d y i n g by us s i n c e 1 9 7 4 . As shown i n F i g u r e 1, t h i s p r o c e s s i s from sodium h y d r o x i d e c o o k i n g o f c h i p s and d e f i b r a t i o n o f cooked c h i p s f o l l o w e d by t h e r e p e a t e d t r e a t m e n t s w i t h chemi*c a l s such as c h l o r i n e , c h l o r i n e d i o x i d e and sodium


180

CELLULOSE AND FD3ER SCIENCE

hydroxide for a s e l e c t i v e d e l i g n i f i c a t i o n . For an example, t h e r e i s C - E - H - E - D - E - D sequence a f t e r p r e cooking. P u l p y i e l d i s 6 0 - 7 0 % depending on the p u l p i n g c o n d i t i o n s , and the spent l i q u o r i s w h o l l y r e c o v e r ed, c o n c e n t r a t e d and b u r n t t o o b t a i n s m e l t of sodium c h l o r i d e and sodium c a r b o n a t e . Sodium c h l o r i d e i s s u b j e c t e d t o e l e c t r o l y s i s t o produce c h l o r i n e and sodium h y d r o x i d e . C h l o r i n e i s used t o produce c h l o rine dioxide. The advantages o f t h i s p r o c e s s a r e i n low t e m p e r a t u r e p u l p i n g under normal p r e s s u r e , no o f f e n s i v e odor l i k e k r a f t p r o c e s s and f r e e c o n t r o l l i n g o f p u l p y i e l d depending on the p u l p q u a l i t i e s r e q u i r e d . And the p o l l u t i o n load i s also quite small. However, h i g h power consumption and c o r r o s i o n o f the r e c o v e r y e q u i p ment s h o u l d be p o i n t e t h i s process. Paper t e n d s t o be low i n o p a c i t y and t e a r i n g s t r e n g t h , because p u l p c o n t a i n s much h e m i cellulose. Flow c h a r t o f the HOPES p r o c e s s w i l l be shown i n Figure,2. T h i s p r o c e s s i s from two s t a g e p u l p i n g w h i c h i s from sodium h y d r o x i d e t r e a t m e n t a t Ί 6 0 - 1 7 0 ° C and sodium h y d r o x i d e - o x y g e n t r e a t m e n t a t 1 2 0 - 1 3 0 ° C under oxygen p r e s s u r e l e s s t h a n 1 Okg/cm . A modified Kamyr d i g e s t e r i s t o be a d o p t e d . Spent l i q u o r i s s u b j e c t e d t o a wet combustion p r o c e s s t o decompose o r g a n i c m a t t e r s and t o r e c o v e r sodium c a r b o n a t e . Pulp y i e l d i s s a i d t o be 2 - 3 % h i g h e r t h a n k r a f t p u l p and pulp strength equivalent to k r a f t pulp i n breaking l e n g t h and b u r s t s t r e n g t h and t o s u l f i t e p u l p i n t e a r strength. Toyo P u l p Company announce t h a t t h e y have a f a i r p r o s p e c t o f i n d u s t r i a l i z a t i o n and a 50 t/D p l a n t i s now undr c o n s t r u c t i o n . Flow c h a r t o f a l k a l i - m e t h a n o l p u l p i n g p r o c e s s i s shown i n F i g u r e 3 . Wood c h i p s a r e cooked w i t h 4 0 % methanol i n aqueous sodium h y d r o x i d e or sodium c a r b o nate a t the maximum t e m p e r a t u r e o f 1 6 0 - 1 8 0 ° C . The advantages a r e i n about 3~5% h i g h e r p u l p y i e l d t h a n k r a f t p u l p and i n e q u i v a l e n t p u l p s t r e n g t h t o k r a f t pulp. The development o f t h i s p r o c e s s depends on methanol p r i c e . I t i s worth n o t i n g that a part of methanol comes from wood c o n s t i t u e n t s . E n v i r o n m e n t a l p r o t e c t i o n s i t u a t i o n The p u l p and paper i n d u s t r y has t o meet a n t i - p o l l u t i o n s t a n d a r d s s e t by the government. I t i s assumed t h a t the g o v e r n ment w i l l s h i f t i t s c o n t r o l system from BOD and COD t o TOD and TOC, and a l s o from ppm base t o t o t a l l o a d base of p o l l u t a n t s . F u r t h e r m o r e , the l o c a l a u t h o r i t i e s s e t the r e g u l a t i o n f o r the o f f e n s i v e odor o f k r a f t m i l l .



NAKANO

(Chip)

NaClOa Electrolysis

Softening & . /MnHV* n

NaClOa*

! NaCl

(CÎO2J-—->(Cli>(HCI) (Hj)

,ΟΕ-Η-Ε-Ϊ

KCIOI)->(NaClO>-

'D-E-D /

Lignin removal

(Cl > 2

\k lectro ly s l s f - - - - K N a O H f / KiÀr 1 \

(NaCl)
, 50 times 8T°F, (30°C), 50 times 200 hrs. 2 W F , (120°C), k8 hrs. 0

C o i l Test (times ) 5 5 5 5 5 5 5 5 5

Electro-Conductive Fiber (Selmec) After several years of extensive researches, Kuraray Co. succ e s s f u l l y invented special electro-conductive fiber and developed a series of t e x t i l e goods named Selmec, which had durable properties of high electroconductivity and s t a t i c elimination (^,5_). The principle of making such a f i b e r i s to give nickel plating on the surface of organic f i b e r by the process of nonelectrolytic plating. This p r i n c i p l e i s as same as that used to give metal p l a t ing on the surface of p l a s t i c s . But i n the case of f i b e r , the sur face area per unit weight i s remarkably large, so the velocity of metal plating reaction i s so high that the plating bath become un stable and the production of commercial scale i s impossible. Kuraray Co. solved successfully t h i s problem, obtaining very stable nonelectrolytic nickel-plating bath by adding to the bath a small quantity of guanidine, imidazoline or imidazole as s t a b i l i z e r Mercapto benzimidazole was very effective (6). Sodium c i t r a t e as chelating agent and sodium acetate as buffering agent were added to the plating bath (pH=5) which contained nickel sulfate and sodium


262


phosphite (.NaHzPOi). Any organic fiber can he used as basic fiber material. The method suitable to commercial production was establirshed by spraying the plating solution over the skein of f i b e r (7_) · These nickel-plating fibers have tenacity, elongation, Young s modulus, f l e x i b i l i t y , and specific gravity as same as conventional t e x t i l e fibers as shown i n Table VI. They have almost the same ele c t r i c resistance as carbon f i b e r . They have high electroconductivity, a n t i s t a t i c effect and shielding effect for electrostatic induc t i o n . Table VII shows the main usages of Selmec fibers 1

Table VI.

Comparison of Physical Properties of Kuraray ElectroConductive Fiber (K.C.F.) with other Conductive Fibers Metallic Fiber (Stainless Steel)

K.C.F. Strength (g/d) Elongation {%) Young's Modulus (g/d) Moisture Regain (% 20°C, 65#RH) Specific Gravity E l e c t r i c Resistance ( μ Λ cm) 9

3. 15 60 - 95

19000

- 3.5

0

1.5 -- 1.9 1.9

7.9

2.0

6xl0

3

72

Carbon Fiber 1+200 - U500 1.5 - 2 . 0

8 - lOOxlO

2

Table VII. Main Usages of Selmec Fibers Form of Fiber Filament Yarn

Spun Yarn

Staple Fiber

1. 2. 3. 1. 2. 3. k. 5. 6.

Main Usages Electroconductive working suit Shielding cloth for electromagnetic wave Space heater, etc. Static eliminator Antishock glove A n t i s t a t i c blanket A n t i s t a t i c f i l t e r bag A n t i s t a t i c sewing thread A n t i s t a t i c working s u i t , etc.

1. A n t i s t a t i c carpet 2. Other general materials for a n t i s t a t i c a l and s t a t i c eliminating uses

For the purpose of comparison of s t a t i c eliminating property of Selmec with other electroconductive f i b e r s , the discharge s t a r t ing voltage and discharging current wave of the testing fibers we re measured (Figure 9 ) . When the sample were located by 5 cm above the alminum plate (50 χ 50 cm) charged at 10 kV. I t was shown that the discharge starting voltage and discharging pulse of Selmec we re much lower than other electroconductive fibers. Figure 10 shows the effect of Selmec static eliminator. The residual voltages on the charged polyethylene f i l m are measured re lated to the distance (mm) between s t a t i c eliminator and charged


13.

Tsuji

263

Chemical Fibers in Japan S 4) Ο»

Figure 9. Comparison and discharging current wave between Selmec and other electroconductive fibers. (A) Kuraray electro conductive fiber (Selmec); (B) stainless fiber (8μ) 10% blended yarn; (C) stainless fiber (30μ) monofilament; (D) electroconductive resin coated monofilament.

Static eliminator

Static eiectro meter D

P. Ε , Fi If

0 -10 -201

200 Distance between static eliminator and charged body (mm)

Figure 10. Static eliminating effect of Kuraray eliminator (Polyethylenefilm,speed 100 m/min, discharged voltage at the beginning -{-60 kV)


264


body. The r e s i d u a l voltage i s n e a r l y zero at the distance of about 50 mm. Selmec i s s u i t a b l e t o e l e c t r o c o n d u c t i v e working s u i t and acce s s o r i e s . When worker stands under u l t r a high voltage transmission l i n e , the induced current run through human body i s very much decreased by use of Selmec working s u i t , through which almost a l l i n duced current run away. When ordinary working s u i t i s used, the r e l a t i o n i s reversed and the body current i s very much increased. The s h i e l d i n g e f f e c t i s durable to repeated washing. The M a t r i x - F i b r i l Bicomponent F i b e r s (Ecsaine, C l a r i n o or A s t r i n o ) Next, I w i l l introduce some bicomponent or b i c o n s t i t u e n t f i bers made by s p e c i a l spinning t e c h n i c s . One i s an i s l a n d - i n - s e f o r the manufacturing o Figure 11 shows an example of the conjugate spinneret used t o make t h i s s p e c i a l f i b e r (8_). Two kinds of molten polymer, A and B, are conjugated i n the s p i n n e r e t , then many such a two component f i b e r s are again conjugated before they are spun out from the spinneret. Thus, by t h i s double conjugate spinning the filaments are obtained which have the cross and l o n g i t u d i n a l s e c t i o n s s c h e m a t i c a l l y shown i n the f i g u r e . These two components, A and B, may be any polymer, but the combination o f polyamide with p o l y e s t e r , polyamide with pol y o l e f i n , and p o l y e s t e r with p o l y o l e f i n are advantageously used. When the sea component B i s d i s s o l v e d out by s o l v e n t , the f i lament composed of very f i n e microfilaments of A w i l l be obtained. By impregnating of the web composed of the bundle of such m i c r o f i lament with polyurethane, suede l i k e m a t e r i a l s , Ecsaine, can be made. T h e i r m i c r o s t r u c t u r e s are shown i n Figure 12. As shown i n Table V I I I , Ecsaine has reasonable t e n s i l e s t r e n g t h , e l o n g a t i o n , modulus, and high t e a r i n g s t r e n g t h , crease recovery, water vapor and a i r p e r m e a b i l i t i e s , and shows very low shrinkage by water b o i l i n g . They give very s o f t man-made suede or high drape apparel. Another one i s the melt mix-spun f i b e r used t o make a man-made l e a t h e r C l a r i n o ( c a l l e d A s t r i n o i n the United States) made i n Kuraray Co, For the production of t h i s s p e c i a l f i b e r , two kinds o f polymers which have d i f f e r e n t s o l u b i l i t y i n a given solvent are melt mix-spun through a nozzle h o l e . The i s l a n d - i n - s e a s t r u c t u r e of t h i s b i c o n s t i t u e n t f i b e r i s i n f l u e n c e d by various f a c t o r s . Figure 13 shows the r e l a t i o n of mixing r a t i o and v i s c o s i t y r a t i o with the forma t i o n of i s l a n d and sea phases of the mix-spun f i b e r composed of nylon 6 and p o l y s t y r e n e . In the region under the curve, the i s l a n d phase i s composed of nylon 6, and i n the r e g i o n over the curve the i s l a n d phase i s p o l y s t y r e n e . Therefore, when polystyrene i s removed by solvent e x t r a c t i o n , e i t h e r porous or f i n e f i b e r bundle both composed o f nylon 6, as shown i n Figure ih and 15, w i l l be obtained depending on the s t r u c t u r e of the melt mix-spun f i b e r s . Figure l6 shows the s t r e s s - s t r a i n curve of nylon,6 s p e c i a l f i b e r a f t e r e x t r a c t i o n of polystyrene sea phase. This s p e c i a l nylon 6 f i b e r has


13.

Tsuji

Chemical Fibers in Japan

Figure 11. An example of the conjugate spinneret

Figure 12. Microstructure of Ecsaine and natural suede


265

266


10 7 5 3 - \ Island Phase Polystyrene Island Phase Nylon 6

05 03

0.1 β

9ίο %ο %ο %ο %ο 7

6

5

Mixing ratio

4

%o %o

z

2

Nylon6/Polystyrene

Figure 13. The relation of mixing ratio and viscosity ratio with the formation of island and sea phases of the mix-spun fibers composed of nylon 6 and poly styrene

Porous f i b e r

Fine f i b e r bundle

Figure 14. Mix-spun and solvent extracted fibers for Clarino. (left) Porousfiber;(right) finefiberbundle.


13.

Tsuji

267


Figure 15. Mix-spun and solvent

0

20

40 Elongation

60

80

(%)

Figure 16. Stress-strain curve of the special fiber of nylon 6 after the extractive removal of the sea phase component


268


substantially the same characteristics as those of conventional nylon 6 f i b e r . Table V I I I .

Comparison of the Properties Suede Ecsaine Thickness (mm) Ο.85 App. Density (g/cm ) 0.27 Tensile Strength (kg/cm) 7 . 9 x 6 . 7 Elongation {%) 86 χ 105 I n i t i a l Modulus (kg/cm) 7.5 χ k.h Tearing Strength (kg) 2.9 χ 3.0 Abrasion Resistance g ^ (weight decrease %) Crease Recovery (% Dry 89 82 Wet 86 χ 82 Water Vapor Permea 30.9 b i l i t y (mg/cm -hr) Air Permeability (cc/cm-sec) Shrinkage by Water . 0.9 Boiling (%)

of Ecsaine and Natural Sheep Suede 0.83 0.60 20.0x6.6 35 * 37 26x7.3 1.0 χ 1.1 18 U

3

69 67 29 x 27 29.8

2

Q

2

0

x

0

h

9

χ

^ U

5

Needie-punched web of these special fibers i s impregnated with polyurethane resin to make sheet materials. Porous fibers free of island phase are used for Clarino of r e l a t i v e l y hard type, and the bundles of fine fibers free of sea phase are used to make Clarino sheet for clothing and other soft application. Figure 17 and 18 show the sectional view and surface of Clarino. The stiffness or f l e x i b i l i t y of the sheet material i s i n f l u enced to great extent by the condition of bond between fiber and resin. When one of the components i n the fiber mat or web i s ext racted with a solvent before the impregnation with resin dope, a high density, high tenacity, rather s t i f f sheet i s obtained, be cause the fiber and resin closely contact as seen i n Figure 19.A. But i f the fiber web i s impregnated at f i r s t with resin dope and coagulated before the removal of one fiber component by extraction, the bond between fiber and resin i s broken by solvent extraction, thus leaving a f l e x i b l e sheet (Figure 19.B). In the type C method one of the component fibers i s dissolved to impregnate the web and followed by coagulation. Since the extracted polymer dose not need to be recovered, t h i s method has a commercial advantage. However, i t i s said i n view of the latitude of the resin selection, quality, productivity and other factors, Clarino i s manufactured b a s i c a l l y by method B. Figure 20 shows the stress-strain curves of various sheet materials. The curve of Clarino i s similar to that of c a l f suede.


13.

Tsuji

269


Figure 17. Cross section of C hrino

Figure 18. Surface of Clarino



Figure 19. Three types of the sheet material from special fiber and polyurethane

A

Figure 20. Stress-strain curves of various sheet materials. (A) Polyester oriented film; (B) paper; (C) cotton suede for manmade leather; (D) plain weave fabric; (E) natural leather (kip); (F) Chrino; (G) calf suede for apparel; (H) needle-punched nonwoven; (I) soft rubber.


13.

271


Tsuji

Emulsion Mix-Spinning lymers

of Polyvinyl Alcohol and Other Synthetic Po

Professor I. Sakurada, Professor S. Okamura and Tsuji et a l . i n Kyoto University developed more than f i f t e e n years ago a new t e chnic of the emulsion mix-spinning of polyvinyl alcohol (PVA) with other various synthetic polymers (9-12). Water dispersions of various synthetic polymers are mixed with aqueous solution of PVA and spun into a concentrated aqueous solu t i o n of sodium sulfate. Fibers thus obtained are heat-stretched, heat treated and formalized s i m i l a r l y to the ordinary PVA fiber (Vinylon or V i n a l ) . As an example, Figure 21 and 22 show the cross and longitudi nal section of a mix-spun PVA fiber containing p o l y a c r y l o n i t r i l e (PAN) emulsion p a r t i c l e s the PAN particles are ber i s heat-stretched at about l80°C, these PAN particles are ad hered together, and stretched and oriented along fiber axis. This i s shown by x-ray d i f f r a c t i o n diagram of such fiber as shown i n Figure 23. The d i f f r a c t i o n pattern shows that both PVA and PAN mo lecules take orientation along the fiber axis i n the mix-spun f i ber. This aspect i s also seen i n Figure 2h for PVA-polyethylene mix-spun f i b e r . I f PVA i s removed out by formic acid after heatstretching, t y p i c a l f i b r i l structure of polyethylene remains. Thus, PVA fibers containing as high as equal quantity of v a r i ous synthetic polymers such as PAN, polyvinyl chloride (PVC), poly v i n y l acetate (PVAc), polyethylene (ΡΕ), polystylene (PSt), polyvinylidene chloride (PVdC), etc. are obtained. As shown i n Table IX, they show the ordinally l e v e l of tenacity, elongation, modulus and low shrinkage i n hot water. It i s notable that those fibers which contain large quantity of the polymers having low softening or melting temperature such as PVAc, PVC or PE, do not shrink u n t i l about 150°C as shown i n Figure 2 5 . Table IX.

The Properties of Emulsion Mix-Spun Fibers

Mixing Ratio Polymer/PVA PAN pvc

1/6 1/3 i/k 1/2 1/1

PVAc

1/2

PE

1/1 1/2 1/1

Heat Drawing Ratio 3.0 3.8 3.3 2.2 2Λ 2.7 2.7 2.7 3.0

Shrinkage Tenacity i n Hot Wa (g/d) ter {%) 1.0 3.7 5.9 5.2 h.9 3.6 5.6 2.1 3.7

U.15 3.73 5.kh 2.66 2.33 U.09 1.86 2.09 2.39

T

Elong- Young s at ion Modulus (kg/mm ) 2

18.7 21.8 18.7 26.6 26 Λ 18.3 19.2 19. h 19.1

517 509

-

386 301 h91 35h 308 267

This p r i n c i p l e of emulsion mix-spinning i s being u t i l i z e d i n Japan to produce Cordelan of Kohjin Co., which contains about equal


272


Figure 21. Cross section of a mix-spun PVA fiber containing polyacrylonitrile (PAN) emulsion particles (PAN/PVA = 1/4, unheat-stretched)

Figure 22. Longitudinal section of a mixspun PVA fiber containing polyacrylonitrile (PAN) emuhion particles (PAN/PVA = 1/4, unheat-stretched).


13. TSUJI


273

Figure 23. X-ray diffraction patterns of the emulsion mix-spun fiber, acrylic, and PVA fibers.

Figure 24. PVA-polyethylene mix-spun fiber. PVA was removed with formic acid after heat-stretching.


274


Temp. 1.

PM/PV

2.

PE/PV

3.

PVAc/PVA:

( ·c )

2/1

Figure 25. Heat shrinkage of the emulsion mix-spun fibers. (1) PAN/PVA: 2/3; (2) PE/PVA: 1/1; (3) PVAc/ PVA: 2/1.

Figure 26. X-ray diffraction pattern of collagen spun fiber


13.

TSUJI


275

quantity of PVA and PVC and has high flame retardant property. Regenerated Collagen Man-Made Fiber F i n a l l y , I would l i k e to introduce b r i e f l y the collagen manmade fiber developed by Nippi Co. (13). Natural collagen i s an insoluble fibrous protein composed of r i g i d rod-like molecules called tropocollagen. Three subunit polypeptide chains of tropocollagen are held i n h e l i c a l configulation. On the end of tropocollagen molecule there are so-called telopeptide regions i n which the aminoacid composition and h e l i c a l c o n f i g u l a t i on are different from those of the major portion of tropocollagen. The telopeptide regions are recognized as the location of i n t r a and intermolecular crosslinkings. Recently, some methods were introducred to s o l u b i l i z e the insolubl gesting the telopeptid lecular conf igulation. Thus the way to make collagen man-made fiber was developed. Thus the aqueous solution of collagen, the pH of which i s 3-^, can be prepared. Several percent aqueous solution of solubilized collagen i s spun into s l i g h t l y acidic concentrated aqueous solution of sodium sulfate and regenerated collagen fiber i s stretched, d r i ed, and f i n a l l y treated with conventional chrom tanning agent to improve hot water resistance. Collagen spun fiber gives the x-ray d i f f r a c t i o n pattern simil a r to native collagen fiber as shown i n Figure 26. Collagen spun fiber has excellent dry and wet tenacity compared with other regenerated protein fibers as shown i n Table X. I t does not shrink i n water u n t i l near to 100°C. Collagen spun fiber i s considered to have low antigenicity, and various medical uses are being developed, such as surgical suter, a r t i f i c i a l skin, a r t i f i c i a l tendon, etc. Table X. Physical Properties of Collagen Spun Fiber Treated with Chrome Tanning Agent Denier Tensile Dry Strength (g/d) Wet Elongation (%) Dry Wet Young's Modulus (kg/mm ) Knot Strength (g/d) Melting Temperature (°C) Shrinkage Temperature in Water (°C) 2

1 - 5 5 - 6 3 - h 18 - 22 11 - 13 6oo - 650 3.0 - 3.5 200 - 220 90 - 100

Ac knowledgement s I wish to thank Toyobo Co., Kuraray Co., Unitika Co., Toray Co. and Nippi Co. for t h e i r presentation of the h e l p f u l reference materials .


276


Literature Cited 1. Morimoto, S., "Silk-Like Fiber K-6 (Chinon)," Ind. Engin. Chem. (1970) 62, No. 3, 23-32. 2. Nagai, Ε., "Toyobo Flame Retardant Polyester Fiber—Heim," Sym posium on Textile Flammability, Charlotte, N.C., Apr. 18,1974. 3. Watanabe, Κ., Kato, Κ., "Production of Flame Retardant Polyes ter Fibers with Chemically Modified Polymer," 14 International Chemiefaser Tagung, Dornbirn, Austria, Sep. 1975. 4. Nasuno, Α., Bessho, Y., "Electrically Conductive Fiber," J.Text ile Machinery Soc., Japan, Text. Engin. (1973) 26, No. 1, 4957. 5. "Textile Goods Controlled Static Electricity—SELMEC," J. Soc. Fiber Sci. Tech., Japan (1973) 29, No. 7, P233-239. 6. Igarashi, R., Bessho sition of the Bat Pat. 787,039 (Sep. 16, 1975), Appl. May 9, 1970. 7. Maegawa, M., Morioka, H. (Kuraray Co.), "Production Method of Metal Plated Fiber," Japan Pat. 792,749 (Oct, 24, 1975), Appl. Oct. 14, 1971. 8. Okamoto, Μ., Watanabe, K., Nukushina, Y. (Toyo Rayon Co.), USP 3,531,368,(Sep. 29, 1970). 9. Okamura, S., Yamashita, T, "Studies on the Emulsion Spinning," Annual Rep. Inst. Chem. Fibers, Kyoto Univ. (1955) 12, 60-75. 10. Horiuchi, Υ., Mori, N., Kitamaru, R., "Studies on the Emulsion Spinning," (1),(2), J. Soc. Fiber Sci. Tech., Japan (1959) 15, 78, 82. 11. Tsuji, W., Kitamaru, R., Ochi, M., Ko, Ε., Mori, Ν., "Emulsion Mix Spinning of Polyvinyl Alcohol Fiber," (1),(2), Annual Rep. Inst. Chem. Fibers, Kyoto Univ. (1959) 1 6 , 23 ; ibid. (1960) 17,39. 12. Sakurada, I., Tsuji, W., Mori, N., Kitamaru, R., "Method to Im prove the Quality of Polyvinyl Alcohol Synthetic Fiber," Japan Pat. 314,297 (Mar. 14, 1964), Appl. Sep. 1 6 , 1958. 13. Utsuo, Α., "Some Aspects on the Properties and Use of Collagen Fiber," Chemistry of Leather (1973) 19, 117-133.


INDEX A Abrasion resistance, flex Acid(s) catalysis, specific esters of cellulose mixed Acoustic behavior studies Acoustic technique, swept-frequency Acrylic acid Acrylonitrile fiber mix-spun wit casein (chinon) Activation energies, apparent Active species in grafting copolymerization Additives on paper characteristics, influence of resin and polymer .... Adhesive(s) P P E as an Alkali methanol pulping flow chart ... Analytical technique, new Anti-pollution equipments in pulp and paper industry Argentina newsprint from willow and poplar in , Artificial polymers in paper technology Ash content Australian developments in paper science and technology

22 210 13 18 227 229 18 25 209 20 64 40 51 181 188 182 120 93 62 50 134

Β Bagasse 122,124,125 losses in bulk storage of whole 100 in Mexico and Peru, newsprint from 98 newsprint 98,107 manufacture, commercial 102 as sugarmill fuel 98 tissues 100 Balsam 81 Basket method for flammability tests 258,259 Beating degree in pulps from spruce, reed, and straw 43 Beating rate vs. beating degree 49 Beech biometrical data for 48 chemical composition of 52 pulp, bleached 53 pulp mixed with spruce fir pulp 47

Bewoid glue 50 BIED-treated cotton fabrics 22 Biometrical data for beech and spruce fibers 48 Birch 184 in sulfate pulping 168 Bleaching of the pre-hydrolyzed pulp 100 Bleaching, single stage 92 Board products, destination of Canada's 150 Bolivia Branch polymers, composition of Brazil Eucalyptus plantations in newsprint from Eucalyptus in Breaking length variation, suspension strength vs. fibrous composition strength retention Brightness of the groundwood

121 24 121 90 89 187 55,57 45 22 88

C Calcium carbonate, retention yield variation of 58 Calorimetric analyzer 188 Canadian capacity of kraft pulp 155 chemical pulp 158 developments in fiber science 219 mechanical pulp 152 newsprint 149,155 paper and board products 150 paper grade market pulp 150 pulp and paper industry 147 Capacity substitution 152,155,158 Capital cost of bleached kraft mill .158,159 Carbohydrates of the spent sulfite liquor, protein production from .. 167 Carpet fibers, triacetate polypropylene 220 Carpet yarns, celanese 224 Casein (chinon), acrylonitrile fiber mix-spun with 254 Catalyst(s) in the cross-linking cotton, metal ion 210 HC1 as most effective 213 hydroxonium ion 214 mixed metal salt 213,214 specific acid 210 Catalytic activity, sequence of 213

279


280


Celanese carpet yarns 224 polypropylene 222 triacetate 222 Cell position on flexibility index, influence of 49 Cellobiose, irradiated 25,26 Cellulose 1 acetate fibers, production of 5 crystalline structure of 6,10 derivatives crystalline structure of 6 graft copolymerization onto 20 synthesis of 13 equatorial diffractions of N a 16 esters, composition of 16 fiber finishing in Switzerland 197 graft copolymerization onto 20 irradiated 2 wood 2 in Japan 3,29 and meridional diffractions 9 new solvents for 11 in paper technology, chemically modified 62 research in Switzerland 197 with reversible cross-linkings, synthesis of 17 synthesis of unsaturated acid esters of 13 triacetate, graft copolymerization of styrene onto 27 trinitrate 7,10 Cellulose II, crystalline structure of .... 7, 9 Cellulosic fibers in paper converting, modified 60 raw materials in Latin America, newsprint from 80 resources, exploitation of local 130 Chain structure of cellulose trinitrate 7 Chelate complex 215 Chemical fibers, synthetic papers from 66 pulp, Canadian 158 pulp, production of 162 treatment 105 Chile 122 newsprint from Pinus radiata plantations in 84 Chip-feeding system 165 Chip grinding process 95 Chrome tanning agents, collagen spun fiber treated with 275 Citric acid as co-catalyst 215 Clarino 269 matrix-fibril bicomponent fibers 264 mix-spun and solvent extracted fibers for 266, 267

Clay-coated type 77 Co-catalysts, tartaric acid or citric acid as 215 Coil test, 45° 260 Collagen man-made fiber, regenerated 275 Collagen spun fiber 274,275 Colophony glue 53 Commercial speeds and output 118 Commercial trials 95 Compressibility of preconsolidated papers 53 Computers, use of 188 Conductivity, superficial 53 Coniferous forest in Mexico, newsprint from natural 87 Conifers, low resin 81 Conjugate spinneret 265 Continuous digester 154,158,159 Cost(s) of bleached kraft pulp mills 158,159 capital 186 manufacturing 108,114 Cotton BIED-treated 22 with formaldehyde, rate constant of cross-linking 212 metal ion catalysis in the cross-linking of 210 poplin cross-linked with formaldehyde and D M E U 205 research and development, Swiss .... 200 Crease recovery angle, dry 205 Creep of fibers 256 Cross-linked fabrics, properties of 203 Cross-linked with formaldehyde and D M E U , cotton poplin 205 Cross-linking cotton with formaldehyde 212 of cotton, metal ion catalysis i n the 210 reaction 211 synthesis of cellulose with reversible 17 Crotonic acid 18 Crystalline and non-crystalline regions, interface between 236 Crystalline structure of cellulose 7, 9,10 Cuba 122 Cusi process 102,104 Cyanoethylated pulp, papers from 61

D Defibration mechanical process Deformation, Hookean De-inked stock in Mexico, newsprint from


92 105 164 242 119

INDEX

281

De-inking mill 119 Demand of pulp and paper 177 Depithing 123 strong 101 systems, wet 104 Diffractions cellulose and meridional 9 of cellulose trinitrates, equatorial ... 10 of Na-cellulose, equatorial 16 Digesters, continuous 154,158,159 Digestion, mild short-cycle 105 Dimensional variation 55 Dimethylacrylic acid 18 Disc milling, two stage 101 Discharges, accidental 191 Discharges, temporary 192 Dissociation constant 18 D M E U , cotton poplin cross-linked with 20 Dry papers, strength variation Dye uptake 242 Dyeing and pore size distributions .... 245

Economic situation of pulp and paper industry in Japan 172 Ecsaine—matrix-fibril bicomponent fibers 264,265,268 Ecuador 124 Electroconductive fiber(s) 263 Kuraray 262 selmec 261 Electrokinetic potential 50 Electrolyte quantity 45 Electron microscopy 234 Eliminator, Kuraray 263 Elongation, difference of 242 Elongation, fiber wool 242 Emulsion mix-spun fibers 271-273 Energy consumption 189 Environmental care project, S S V L 191 problems 191 protection situation 180 Equatorial diffractions of cellulose trinitrates 10 Equatorial diffractions of Na-cellulose 16 Ester ratio 17,18 Esterification in fiber form 10 Esterification process, Toyobo direct.. 255 Ethylene oxide, polyester production from 252 Eucalyptus 134 in Brazil, newsprint from 89 plantations in Brazil 90 Exclusion, solute 234

F Fabric(s) BIED-treated cotton 22 finishes, fluorochemical 223 properties of cross-linked 203 treatment, ideal 226 Fatigue behavior 240,244 Felted sheet structure 187 Fiber(s) absorption of powder on the surface of pulp 78 beech and spruce 48 collagen spun 274,275 creep of 256 electroconductive 262,263 finishing in Switzerland 197 form, esterification in 10 heim staple 257 modulus of 256 hollow 33 in Japan, chemical 252 Kuraray electroconductive 262 length in pulps from spruce reed and straw 43 mix-spun 271,273 with casein (chinon), acrylonitrile 254 for Clarino 266,267 nylon-6 and polystyrene 266 PVA 272 non-wood 142 non-woody plant 178 nylon 241 in paper converting 60 porosity, polyester 247,248 porosity, wool 247 production of rayon and cellulose acetate 5 production, viscose 168 properties of rayon staple 31 regenerated collagen man-made 275 science 195 Canadian developments i n 219 secondary 130 selmec—electroconductive 261 structure and interactions in the 235 synthetic papers from chemical 66 texture of 233 triacetate polypropylene carpet 220 type, mineral 77 wool elongation 242 Fibril bicomponent fibers, matrix264 Fibrous composition vs. breaking strength 45 Fibrous material(s) 40 and paper products, relationships between 39



282

Groundwood Filament, high modulus vinylon brightness of the 88 (vinal) 253 capacity 85 Filament yarn, heim 257 pulp 163 Film Scandanavian 86 base type demand 74 type pulp 96 base type synthetic paper age 73 type, pigmented 75, 77 Finishes, fluorochemical fabric 223 H Finishing in Switzerland, cellulose fiber 197 Hardwoods, mixed tropical 140 Finland 95 Hardwoods, pulp from 47 Finnish pulp and paper industry 162 HC1 as most effective catalysts 213 Fir pulp, beech pulp mixed with Headbox, high consistency 166,187 spruce 47 Heartwood, dark 87 Flame Heat of wetting 242 retardancy of heim 261 Heim retardant elements, residual flame filament yarn 257 time vs 260 flame retardant polyester fiber ... 254, 261 retardant polyester fiber (heim Flammability tests, basket method for 259 Holes 237 Flex abrasion resistance 22 Hookean deformation 242 Flexibility index, influence of H O P E S flow chart 181 cell position on 49 Hydroxonium ion, catalysis by 214 Flour 101 Fluorochemical fabric finishes 223 I Fluorochemicals 224 Foamed sheet age 72 ICS process, Bobtex 221 Forest residues 142 ICS yarn, three-component 221 Forestation program 89,93 Imports by Latin America, Forests in Mexico, newsprint from newsprint 130 natural coniferous 87 Impregnation conditions 91 Formal 210 Infrared spectra of monofilaments 227 Formaldehyde, cotton poplin Interface between crystalline and cross-linked with 205, 212 non-crystalline regions 236 Formers, twin-wire 153 Irradiated cellulose and cellobiose 25 Fractionation after cooking 105 Irradiated wood cellulose 22 France, textile research in 232 Irradiation to viscose process, Fuel, bagasse as sugarmill 98 application of 29

J

G Glucose, radicals in Glue, Bewoid Glue, colophony Graft copolymerization active species in onto cellulose and cellulose derivatives stereoregularity of polymers formed in of styrene onto cellulose triacetate .. Grafted polymers, composition of polymers, molecular weight distribution and the number of polystyrene Grinding process, chip

26 50 53 20 20 28 27

Japan cellulose in cellulose industries in chemical fibers in pulp and paper industry in anti-pollution equipment in economic situation of synthetic paper technology in Jari project Jylhâ-finer

24 28 32 95

3 29 252 171,172 182 172 72 90 164

Κ Kaolin Kidney, artificial Klabin


50 32 91

283

INDEX

Kraft pulp 96 Canadian capacity of 155 mills, capital cost of bleached 158,159 Kuraray electroconductive fiber 262 Kuraray eliminator 263

L Latin America, newsprint from cellulosic raw materials in consuming countries i n demand in potential in production capacity in Latin America, supply of newsprint imports by Length, breaking Length variation, suspension breaking Lignin compounds Liquid repellency, surface conditions for Load-strain behavior, wool Local cellulosic resources, exploitation of Local modulus

80 129 127 126 81 130 187 55 16 224 241 130 241

M Magnesium chloride 213 Magnesium tartrate 213 Man-made fibers, regenerated collagen 275 Materials throughput for trials 117 Matrix-fibril bicomponent fibers 264 Mechanical defibering 105 properties of BIED-treated cotton fabrics 22 pulp 164 Canadian 152 refiner 151 Melamine addition 55 Mercerization 16 Mercury porosity 234 Meridional diffractions 9 Metal ion catalysis in the crosslinking cotton 210 Methacrylic acid 18 Methanol pulping flow chart, alkali.... 181 Mexico 125 newsprint from bagasse in 98 de-inked stock in 119 natural coniferous forests in 87 projects in 106,114 Mill(s) based on wood and waste paper 125 bleached kraft pulp 159

Mill(s) (Continued) capital cost of bleached kraft 158 closing paper 192 de-inking 119 equipment, pulp 96 paper 99 Milling, two stage disc 101 Mineral fiber type 77 Mix-spinning of synthetic polymers, emulsion 271 Mix-spun fibers for Clarino 266,267 emulsion 271,273 of nylon-6 and polystyrene 266 PVA 271,272 Mixed acids 18 Mixed metal salt catalysts 214 Molecular weight distribution of Monofilament holder infrared spectra of polypropylene

229 227 230

Ν Na-cellulose, equatorial diffractions of 16 Newsprint from bagasse 102,107 in Mexico and Peru 98 Canadian 155 capacity 89,120 from cellulosic raw materials in Latin America 80 consuming countries in Latin America 129 from de-inked stock in Mexico 119 demand in Latin America 127 destination of Canada's 149 from Eucalyptus in Brazil 89 imports by Latin America, supply of 130 from natural coniferous forests in Mexico 87 from Pinus radiata plantations in Chile 84 potential in Latin America 126 production capacity in Latin America 81 sheet, single-furnish 165 supply 127 from willow and poplar in Argentina 93 Nonfibrous components of the wood, utilization of the 167 Non-wood fibers 142 Non-woody plant fiber 178 Nordmiljo 80 193 Nylon fiber 241 Nylon-6, mix-spun fibers of 266



284

Ο Oil repellency Operations Output, commercial Oxidation treatments Oxygen index of P E T / G F P blended yarn Ρ

226 41 118 22 259

Papermaking trials 113 Parana pine 91 Pekilo process 167 Penetration index, influence of pulp addition on 46 Peroxide concentration 27 Perturbators 236 Peru 125 newsprint from bagasse in 98 projects in 106,114 P E T / G F P blended yarn 259 P F P flow chart 181 Phosphorus content of P E T / G F P blended yarn 259 PHU-project 194 Pigmented film type 75,77 Pigmented type synthetic paper age, highly 74

Papel presna 95 Paper(s) age, film base type synthetic 73 age, synthetic pulp and highly pigmented type synthetic 74 board 162 characteristics 41 determination of 40 influence of resin and polyme additives on 64 Pinus radiata plantations in Chile 84 from chemical fibers, synthetic 66 Plant fiber, non-woody 178 converting, synthetic polymers and Plant, pulp modified cellulosic fibers in 60 addition from annual 44 from cyanoethylated pulp 61 from annual 42 grade market pulp, Canada's 150 on paper porosity, influence of industry addition of 46 Canadian 147 Pollution Finnish 162 abatement in pulp and paper mills 179 Japanese (see Japan, paper free pulping 179 industry in) problems 179 Swedish 184 Polyacrylonitrile emulsion particles, influence of pulp derivative on mix-spun P V A fiber containing .. 272 properties of 63 Polyester 246 mill(s) 99 fiber (heim), flame retardant 254 based on wood and waste 125 fiber porosity 247,248 closing 192 production 252 pollution abatement i n 179 Polyethylexyl methacrylate 226 physical-mechanical properties of Polymer(s) grades of 44 additives on paper characteristics, porosity 46 influence of 64 preconsolidated 53 emulsion mix-spinning of polyvinyl production of 162 alcohol and other synthetic 271 products formed in graft copolymerization ... 28 Canada's other 150 grafted (see Grafted polymers) classification of 152 in paper converting, synthetic 60 relationships between fibrous in paper technology, artificial and materials and 39 synthetic 62 relations, p u l p 45 Polymerization process, Toyobo direct 255 science 37 226 Australian developments in 134 Polymethyl methacrylate 226 sizing degree of 57 Polyoctyl methacrylate fibers 220 strength variation of wet and dry .. 54 Polypropylene carpet 230 supply and demand of 177 Polypropylene monofilament Polystyrene, grafted 32 technology, artificial polymers, Polystyrene, mix-spun fibers of 266 chemically modified celluloses, 270 and synthetic polymers in 62 Polyurethane waste 125,178,182 Polyvinyl alcohol, emulsion mixspinning of 271 Papermaking materials 135


285

INDEX

Poplar in Argentina, newsprint from .. 93 Pulp(s) (Continued) raw materials, future shortage of 175 Poplin cross-linked with formaldehyde raw materials and production and D M E U , cotton 205 in 1903 174 Pore size distributions 245 reed 43,45 Porosity refiner mechanical 151 mercury 234 spruce 43,45 on paper 46 straw 43,45 polyester fiber 247,248 supply and demand of 177 wool fiber 247 synthetic 74 Powder on the surface of pulp fiber, for viscose fiber production, absorption of 78 dissolving 168 P P E resin addition 50,51,53,55 142 Preconsolidated paper 53 Pulping alkali methanol 181 Pre-hydrolysis effect 123 birch in sulfate 168 Pre-impregnation system, multi-stage 104 changeover from sulfite-to-sulfate .. 165 Project potential 126 development of pollution free 179 Protein production from carbohylines, thermomechanical 164 drates of the spent sulfite liquor .. 167 Pulp(s) addition P V A fiber, mix-spun 272 from annual plants 42,44 on penetration index, influence of 46 Q of soft wood 50 beating degree, fiber length, and Quarpel treatments 226 specific surface of 43 beech pulp 47,53 R bleached beech 53 Radicals, decay of 25 sulfate 54,163 26 sulfite 93 Radicals in glucose and cellobiose 213 bleaching of the pre-hydrolized 100 Rate constants of cross-linking cotton with Canadian formaldehyde 212 chemical 158 mechanical 152 Raw material future shortage of pulp 175 paper grade market 150 in 1903, pulp 174 cyanoethylated 61 shortage 163,175 derivative on properties of paper, utilization of wood 163 influence of 63 Rayon fibers, production of 5 fiber, absorption of powder on the fibers 31 surface of 78 Rayon staple 22 groundwood 96,163 Reduction treatments 42,45 from hardwoods 47 Reed pulp beating degree, fiber length, and at a higher yield, production of 164 specific surface i n 43 industry 151 Canadian 147 Refiner mechanical pulp 163 Finnish 162 Reforestation program Japanese 171,172,182 Regenerated collagen man-made fiber 275 85 "Swedish 184 Reinforcing stock Resin kraft (see Kraft pulp) addition, P P E 50,55 mechanical 164 additives on paper characteristics, mill equipment 96 influence of 64 mills, population abatement i n 179 conifers, low 81 on paper porosity, influence of content, high 87 addition of plant 46 PPE 53 -paper relations 45 178,182 production of chemical 162 Resource developments products, classification of 152 Resources, exploitation of local project, T194 cellulosic 130



286

Structure (Continued) of cellulose trinitrate, chain 7 and interactions in the fiber 235 Styrene onto cellulose triacetate, graft copolymerization of 27 S Suede, natural 265,268 Sugarmill fuel, bagasse as 98 Sawdust 142 Sulfate Sawmill residues 141 process 164 Scandanavian groundwood 86 pulp, bleached 54,163 Sea phase component 267 pulping, birch in 168 Secondary fibers 130 pulping, changeover from sulfite-to- 165 Selmec—electroconductive fiber 261 Sulfite Sheet liquor, protein production from age, foamed 72 spent 167 forming method, high consistency .. 186 pulp, bleached 93 materials, stress-strain curves of 270 -to-sulfate pulping, changeover structure, felted 187 from 165 Single-furnish newsprint sheet Sizing degree 45,5 of papers 57 Surface conditions for liquid Solute exclusion 234 repellency 224 Solvent extractedfibersfor Surface in pulps from spruce reed Clarino 266,267 and straw, specific 43 Solvents for cellulose, new 11 Suspension breaking length Sorption under stressing 240 variation 55,57 Speeds, commercial 118 Swedish pulp and paper industry 184 Spinneret, conjugate 265 Swept-frequency acoustic technique .. 229 Spruce 81,184 Swiss cotton research and beating degree, fiber length, and development 200 specific surface in pulps from .. 43 Switzerland, cellulose fiber chemical composition of 52 fiinishing in 197 fibers, biometrical data for 48 Synergetic effect of mixed catalysts .... 213 fir pulp, beech pulp mixed with 47Synthetic pulp 45 paper Spun fiber, collagen 274,275 age, film base type 73 SS linkages 22 age, synthetic pulp and highly SSVL environmental care project 191 pigmented type 74 Stereoregularity of polymers formed from chemical fibers 66 in graft copolymerization 28 technology in Japan 72 Stokes-Einstein equation 202 polymers Storage of whole bagasse, losses in emulsion mix-spinning of bulk 100 polyvinyl alcohol and other .. 271 Straw, beating degree,fiberlength, in paper converting 60 and specific surface pulps from .. 43 in paper technology 62 Straw pulp 42,45 pulp age 74 Strength, tensile 205 pulp, debut of 74 Strength variation of wet and dry papers 54 Stress-strain Τ behavior 238 194 viscose 241 T-pulp project 168 curves of hollow fibers 33 Talloil curves of sheet materials 270 Tanning agent, collagen spun fiber treated with chrome 275 Stressing, sorption under 240 Tartaric acid 213,215 Structure 136 of cellulose II, crystalline 7,9 Technological changes, post-war Technology (see also specific areas) .. 147 of cellulose and cellulose 156 derivatives, crystalline 6,10 Technology, future

Retention yield variation of calcium carbonate Ritter method

58 123


287

INDEX

Temperature, tenacity of fibers at high ^ Temperature, Young's modulus of fibers at high Tenacity of fibers at high temperature Tensile strength Terephthalic acid, polyester production from Textile research in France Texture and fatigue behavior of fibers investigations of Texturizing, yarn Thermomechanical pulping lines Titanium dioxide Toyobo direct esterification and polymerization process Transitions Tree utilization project, whole Trees of small diameter Triacetate polypropylene carpet fibers Trials, materials throughput for Trials, pilot and commercial Tropical hardwoods, mixed Trunk polymer, molecular weight distribution and the number of grafted polymers per Twin-wire formers machines

W 255 256 255 205 252 232 240 233 234 202 164 58 255 23 141 220 117 95 140 28 155 153 166

U Ultrafiltration rate Utilization of wood raw material

33 163

V Venezuela Vinylon (vinal) filament, high modulus Viscose fiber production, dissolving pulp for process, application of irradiation to processes, conventional and no-aging stress-strain behavior

125 253 168 29 31 241

Warp wrinkle recovery 22 Waste paper 178 mills based on 125 origin of 182 Water consumption, decrease of 179 Waterproofing characteristics 53 Weibull representations 244 Wet papers, strength variation of 54 Wetting, heat of 242 Willow in Argentina, newsprint from 93 Wire, twin 155,166 Wood(s) cellulose, irradiated 22 mills based on 125 pulps, addition of soft 50 raw material, utilization of 163 utilization of the nonfibrous components of the utilizing denser Wool elongation, fiber fiber porosity load-strain behavior Wrinkle recovery, warp

167 138 245 242 247 241 22

Y Yarn(s) celanese carpet heim filament manufacture, novel P E T / G F P blended texturizing three-component ICS Yield, production of pulp at a higher .. Young's modulus of fibers at high temperature

224 257 219 259 202 221 164 256

Ζ Zetha potential


53

Cellulose and fiber science developments: A world view

Cellulose and Cellulose Derivatives (Polymer Science Library)

Cotton Fiber Chemistry and Technology (International Fiber Science and Technology)

Science Education Issues and Developments

Tomb and a View

Tomb and a View

Cellulose Chemistry and Technology

The Ecological World View

The Ecological World View

Regenerated Cellulose Fibres

Flavour Science: Recent Developments

Some Developments in Wittgenstein's View of Ethics

Cellulose. Molecular and Cellular Biology

Biosynthesis and Biodegradation of Cellulose

Crime and Crime Control: A Global View (A World View of Social Issues)

Jeff's View: on Science and Scientists

Natural Acts: A Sidelong View of Science and Nature

New Nanotechnology Developments (Nanotechnology Science and Technology)

Physics and our View of the World

Physics and our View of the World

Services Science: Fundamentals, Challenges and Future Developments

Computer Science Today.. Recent Trends and Developments

Developments in Block Copolymer Science and Technology

Lord of All: Developing a Christian World-and-Life View

Regenerated Cellulose Fibres

Fiber And Your Health

Cellulose and Cellulose Derivatives: Cellucon '93 Proceedings: Physico-Chemical Aspects and Industrial Applications

Teenage Pregnancy: A Global View (A World View of Social Issues)

Domestic Violence: A Global View (A World View of Social Issues)

Women's Rights: A Global View (A World View of Social Issues)

Child Labor: A Global View (A World View of Social Issues)

Cellulose and fiber science developments: A world view

Cellulose and Cellulose Derivatives (Polymer Science Library)

Cotton Fiber Chemistry and Technology (International Fiber Science and Technology)

Science Education Issues and Developments

Tomb and a View

Tomb and a View

Cellulose Chemistry and Technology

The Ecological World View

The Ecological World View

Regenerated Cellulose Fibres

Flavour Science: Recent Developments

Some Developments in Wittgenstein's View of Ethics

Cellulose. Molecular and Cellular Biology

Biosynthesis and Biodegradation of Cellulose

Crime and Crime Control: A Global View (A World View of Social Issues)

Jeff's View: on Science and Scientists

Natural Acts: A Sidelong View of Science and Nature

New Nanotechnology Developments (Nanotechnology Science and Technology)

Physics and our View of the World

Physics and our View of the World

Services Science: Fundamentals, Challenges and Future Developments

Computer Science Today.. Recent Trends and Developments

Developments in Block Copolymer Science and Technology

Lord of All: Developing a Christian World-and-Life View

Regenerated Cellulose Fibres

Fiber And Your Health

Cellulose and Cellulose Derivatives: Cellucon '93 Proceedings: Physico-Chemical Aspects and Industrial Applications

Teenage Pregnancy: A Global View (A World View of Social Issues)

Domestic Violence: A Global View (A World View of Social Issues)

Women's Rights: A Global View (A World View of Social Issues)

Child Labor: A Global View (A World View of Social Issues)

Recommend Documents