r<7) a##li, B^JI^ftW^R/r^JAERI-M u#-r i L-C, ^SefflfcfUffLTv>4 JAERI-M reports, issued irregularly, describe the r~sults results of research works car

Transcription

1 JAERI-M ~AERI-M mm? 7 7 M&K i s *«*itf)ew ^5H H * «* * 4 flf ft flf Japan Atomic Energy Research Institute

2 r<7) a##li, B^JI^ftW^R/r^JAERI-M u#-r i L-C, ^SefflfcfUffLTv>4 JAERI-M reports, issued irregularly, describe the r~sults results of research works carried out in JAERI. Inquiries about the availability of reports and their reproduction should be addressed to Division of Technical Information, Japan Atomic Energy Research Institute, Tokai-mura, Naka-gun, Ibaraki-ken, Japan.

3 JAEEI-M a *m* -ftwrmmm ma ( li 4M 1 6 B 1 ) ^m^in. mam?? y t-m-&ircsl2> &m.m &yucm-tz> % -abh 0 mmtlxid, &&mm 'p-c&mmtlxm,&iki,t mm.fr '<, #***»**«~ 完 水

4 JAERI-M 9481 i Modification of Synthetic Fibers by Radiation-Induced Grafting Kanako KAJI Osaka Laboratory for Radiation Chemistry, JAERI (Received April 16, 1981) The present report describes studies to modify properties of synthetic fibers by radiation-induced grafting technique. This technique was employed since it is considered to be generally applicable to the grafting of a radically polymerizable monomer onto fiber. Three synthetic fibers were used mainly in the present studies; (1) polyester fiber which is ranked as the first in the amount of production in the synthetic fibers at present and is expected to increase in its importance in the future, (2) poly (vinyl chloride) fiber which is inexpensive and fire-retardant, and (3) polyethylene fiber which is not yet used in apparel at present. In order to perform the grafting, the following two methods were studied; one is to graft monomer uniformly in the fiber* preventing homopolymerization of the monomer outside of the fiber, and the other to graft monomer only on the fiber surface. Using these methods, the following experiments were carried out and fairly good results as expected were obtained. (1) In the case of polyester fiber it was intended to make this more hydrophilic and fire-retardant. (2) Concerning to poly(vinyl chloride) fiber experiments were carried out to make the fiber more hydrophilic and simultaneously more heat-resistant. (3) In the case of polyethylene fiber, target was fire-retardance and heat-resistance. Keywords: Radiation, Grafting, Synthetic Fiber, Modification, Polyester, Poly(vinyl chloride), Polyethylene, Hydrophilic Property, Heat-resistance, Plame-retardance

5 JAERI-M g» ws 3w ' -»** - ± i. # y x *? A-ift^ r ^ y *»? y y \ M& 2 2. * y x^ T- /i^ist-v y * ^ y A-aj?? y \- n& r^ y Asmfrxvs *s y ^S5*^7 7 H^L^S!) ^-r^ifi ^ * y x.* T- A-iiHit'^ tr - A- f Q y vv<d?7 y h M& #. y x* 7- /v:ft-"n )fi]i?vy;ij = -A- ^ ^^- y A-8J& & C-,fiT ^ " "'H* $>X.* 7-A- ^7 7 b S-& &% K U * ' ^ ^ *i gtfi 3 fb i <f ; * V x^ -r A-$ g 7**!)gig tr=a-7*^7*4-h>l-y = "-* <D?y 7 b I^Ki rf? 'J x^-r A-;ft JMftft 106 a * y^ftt*^ y x^li^ct ^ IJ»=H*O;37 n ^ r^- y A-ae ^? y tn&rc 2>#vmte = *>mm<d&'g *' Uffiffc tf = A-i(t g'v0t^ 'i A-R*A--y?A ^? 7 H ^ * V&.\t^-*WM~~0 7? 'J A-T? K ;?? 7 b :! MftSitf y x*- u>- y 4 j J > h ^.<o 7? y A-aS?? 7 h S-n- 167 X # 186 tg Jg 191 *** StfC 88-*& WHIR'S 193 m & 194

6 JAERI-M CONTENTS General Introduction 工 n 七 roduction' 日 '" ~ Grafting of Acrylic Acid onto Polyester Fiber 2 2. Grafting of Methacrylic Acid onto Polyester Fiber Properties of Acrylic Acid and Methacrylic Acid Graft Polyester Fibers Grafting of Vinylpyrrolidone onto Polyester Fiber ~. H... H... H." H.., H Grafting of Poly(ethylene glycol) Dimethacrylate and Diacrylate onto Polyester Fabric Radiation-Induced Chlorination of Polyester Fiber Alkali-Treatment of Chlorinated Polyester Fiber Preparation of Flame-Retardant Polyester Fabric by Grafting of Oligomeric Vinyl Phosphonate H H..~. H... H... H H... H... H ~ H... H... l ~ Grafting of Acrylonitrile onto Poly(vinylidene chloride) Fiber Modification of Poly(vinyl chloride) Fiber by Grafting of Acrylic Acid Grafting of Calcium Acrylate onto Poly(vinyl chloride) Fiber Grafting of Acrylamide onto Poly(vinyl chloride) Fiber Grafting of Acrylic Acid onto High Density Polyethylene Filament 16 7 References 186 Summary 1 91 List of the Publications 193 Acknowledgement ; 19 4

7 JABEI-M & m 本 論 文 vc j;,~ いては, 繊 維 κ 所 望 の 性 質 を 付 与 するととを 目 的 として 行 った 放 射 線 グラフト 重?yy t-nstti, mm.m %-?$Lm*>&-?L<t>mmc-it-r%rL^&3s.itfMx%&±s m &:!ib.%&;tlxttmi}xtfr:%%)%%&:-c >2>o Lri»L. ^5? H-&tW5f KMffl tfl^fyy vm&fimmvcmz. $ M\r>%%mA,xmx&m-&%smzmfflLx^2>m&ft& bkpst-c=r«fl-»'v JittJ*5 ^3n-t:^4^*", J ** w«i!i4t*(c^^t. Jfc&iS!^ t J: 5 4 ^7 7 H^K*«W P?i^i(i, HI (c^^k«u!if*3k:* ^-SSA^^S*. H-JCtt, Rl«F(CSffi-t--5iltili^. ***"U '-ilrti>k«llt S^-r*i), 本 3t:W5SKi?^t 研 究 vc j;,~いて ttc n b ^i/s ft S *-ta^j6ifc^(c^^j& & =.?%:,, ^ f *T^7 7 hsjsftjg <*.& ( 5t>i9>&SM^7 7 I- ); j K^^T fctfettftft^fc,, a#, * ^ 3 7 h t«;-ta tt#3ik:s «i5*lt^sj: 5(c, ^57 b«g#-^-#, ^^ ^(C^/f * - "?* # LI '^t fts3fc-*6o l» 0 ^ 7 7hi»fS (l, * * - ft#> fc. #5-iF<!:^77 h«os» : f#«k:*'t^5t, ^?7 >m<dmfr^-e>mmx' ztib<d?yy t-mmv&'sizmmmz&mk&t, ^cmsffstc^cxmrnkm^. &*? 7 h«ii»c0faottji!6j#43nt^a*»*ttwl*.

8 JAERI-M * y x.v-vs't-v?? v~ h (PET) flmi, Sfci^&tfy * ^ ^ A-idiiiifi, ^Bg««i => tlt*ik41sntv>i,o Ztittmtett&K. &&)&Mmifc-f<;n, ifc-froh-t^fi mmmmt LX am L < ^tt» 4#^i w. PET«iii -t Cii3ttt«ftffl*art»* 5 t <..**> & **# *.& t <t * 1ft ilt, T^ 'J *IKAA) &&$;?'9 7 H^4fi4ofc $ *, PET««lfC5J*t-tS»liiS^7 7 hs-g-kbs-tsw^ehikkk^^^otto-ttlttpet ft-itibxhho LfrLmm<D&wt^5mm&i-&$:mfrbn,tiii3., *«^7 7n^ n. -?r atfipetifili^^*^ *-#&ALIi^7fc»&T&S *^^- ga*{eii-t^^ «>*ctt. mmn^m^i,o^m^t^a.bnh 0 -tax^m^tii, PETmm?-??n^ K»»-fr5S:*flffll**WL7k. -tsfct^d-c7j <, mm fcbmzmz.l, vm-tt.m : k i Wr?h 0 x^o/77! «<&«^/65@<7SI9P D P«**L <«7x5/SH ff& 0 «JS-f^^ ^i!jp7)5. AA*S«i*ffl^a&Wi»^7 7 bb"& C;fc«^T**#i; -*- $ «i(i'n AA a;iiib^? 7 H ^ K ^ M, **# y-»- ^s «iftok*3ai(cffl^t>ixa との 章 では r 線 及 び 電 子 線 を 用 いる~ 潰 法 同 時 照 射 モノマーあるいはモノマー 溶 液 κ ポ 'J ^-*SitL7t«:SSTM*Jt Hl^^^7 7 hm^fc&frs-tir.&^feuc j;;&pet8tj #^ A A ^"7 7 h a-&4*-a-& (6(Ea!e^Tx* = >7 A^TJ<^( NH 4 ) 2 Fe(S0 4 i 6 H 8 0 ) : ;

9 JAERI-M m&h'fc 2.1 M.WftbVKi&m i$.wtlxm^fcpetffl.mtffimk&z,7- \"*-s747/'s\-{. 75d/30f ) T *> $>, mm Mt LxTio 2 t 0.5%-^A,T^;E> O ffifflttrkt? *; -^ o.i %-^mw.x sot; tiffi, f?rc *$y - ^ o. I ^TK^mtr sot; -e I mfat&m i±wlm%?kt-%ftm.&lxmmcm i ± a Jp-t^*-^^^ m^^itfflttttjls#^fd^-t Hffl^^o 2. 2?7 7 Y S-& ^7 7 (v. d. G.)sns^i b(dn^bfrm^hm&ib*>h a PET«R*iKJ0.2g*^.#l cmomitrcaft- A A 60%-fcmWLVC*- n<m% MM I 7fe * 4ml fcan/l, mm**i 2 &?$'&kft&km%lfto MM ( ~23t む )rcl~-24 ) f lo~24b5f 時 間 t «8 保 ojfe^k 20 ± 3 t -c 60 Co «C i) r ii*b8wl. Ao flai^kicfl *» 5 TJCT 2«FfHaS» L.AA **#.IJ -* - SttttiL, mftifflnj; S>»o*T**tto^7 7 i- ^ (D) *^to^<, SP-&,» i 5 *fflffi^ PET«itftiiJn Z-frtfOf? 7 \-% (D^)= X 100 JgPETOM ^IbKfi^KT-h 'J 9 A (NaH0O 3 ) 1 ^** &T 80 tlt 3 B#P B 1ffi3S L.» SztcMStT H i i t ^ M A * ' y ^-MffiL.t, t ffl3skj: j), /77hAA(JNaStD^(CS5 ので, 水 洗 後 2~ 弱 酢 酸 水 溶 液 で 80 t:で 1 時 間 処 理 して 元 の 酸 の 形 κ 戻 し. T, zkffiie 2«g^»7K ^T80CTl W1ffliLT%OSOiKIL, NaHC0 3 *««& SSE *^fr ^7 7t*(E) &^367fc 0 A A ^-7 7 n^ra--w.t.**-ij ^- flkttt*gjr ^. B35»f> fliiwl^**. -»**#p *-**w>-c»'fr**iftftflfc98iiu*.&. 2.3 * * * >j» - ^--^ftaijg ihuao^iti, J>**-9- > so. 7k20 (.mitt )<Dg,'&Wc#v -* - * *? I, 30 tjtfloselfcsirtekrfcfli^-cfcssrcjt J>tt*L7ko* CO" 6.59 X 10~ 4 M I /?7h«-&rcafi-t»'frjiiit«iio»* - 3

10 JAEBI-M zmm&mmi, m&m3.2xio 5 Taa/h<D r ffi%m%i-thtls^momw-c^y^hwbetth'ffcl -tt-c. ^?7H^o^cc5ts^, a*oa^«iih»joaa**a^ks*^s*ih«i Table l.l JJ, a* **ffioaa**a#»c«-taa-frj J hjai*tbs-<a:js*-c*4. ~ち( 60 #(gft 容 量 ) AA*ttK^Iij4X l<r 3 mol/2»lt, 3. 2 X 10 5 rad/h iul^t *#BftL-t*fr*fcfl:fcLT 4«ttL4<*oft#ffl4GeI iltsl*. Clear olutionttawfcfci/<,<!:*&< ntfcjmfc-ej, i>, T-fc h >KftAtitt>f«>Ke»ti 8KO#H-48iti 3 ft. Table 1.1 &»* *, g%, *«&# *-:- &«* ttaarc»lt«^* -5:fliiw-*43»*;fljj3:^tf,, *-a^btrls. a**{b -*-a ti がわかった すなわち, *«fc*>93to *% *>, 大 ^^5- «^ici>^-t, 部 分 の 場 合 にないて, 窒 a*«kaa a-&!6sjett,, 素 置 換 後 ~AA の 重 合 が 起 と þ, 水 *K*JL K 対 し Table 1.1 Effect of various metallic salts on homopolymerization of acrylic acid. AA/H2O = 6/4, concn. of metallic salt 4xl0" 3 mol/, sl~ad/h dose rate 3.5x10 s rad/h,, irrad. temp. 24 C. irrad. time, 0.5h. Metallic salt Appearance of solution after irradiation No Gel Hohr's salt Clean solution Feci 2 Clear solution Fez (SO*) : l(neu) 2SCU ->) Feci 3 Gel CuCl Clear solution Cu(NOs)2 Clear solution CuSOk Clear solution CUCI2 Clear solution Ni(NOj) 2 Gel Co(NO j)2 Gel Cr (NO3) 2 -i) Pb(N03)2 -i) LiCl -O 1) polymerization occured 0.5h after N 2 flushing without irradiation. 4 -

11 JAERI-M 9481 &&, m&fc^\r>xit±, mm<d&m}±m&ik±%i&t±2-t>ti-&froaft. urn mm.. r«s -g-wsua*#* & ^ & 1#t>rf» 7 ^,,, '5;*.-'. ^^^ ftj) CO SfijKc, fa^p-zu, ^< KB #y v, ^f Kn*y^*y^(^^ m%f-*-mw.k.0.2%mtolx, 2 0trcfrM, 3. 2X 10 5 radxh jgi:$tflml7fc if-g-, 0.5hT@^*->ttO* #4«L^:. ( re**"), CuC$ ( Cu + ), 0uSO 4 ( Cu 2 + )Kd^t ^^^jftg&^^t ;/7 7 bl^tl?* Table 1.2 RO'Fig. 1.1 IfC^e-^m ( Fe B0 4 (NH 4 ) ) «K5r 4 X l(t 4 ~ 1 X 10" 1 Gel, Clear solut ion ft-^l^t WtT KKI8 Lfc#, Viscous sol ut i on li±mwt")fcffi ftffi ^L, R5*f^ i m*t-b h yfcsatsi *-'J r^ y *-$ a«t5r Dfco Fig.l. l t P :SlT-;T:L7tV$.D : Gfi-?-./5»ib' : e7 * * $ ** Viscous i olution & l^figel (CJSti ttftt^, ^-^S^^SflL^^^^ti. 15 ^ JSItT H^^^JJS^^L, 1 %NaH0O 3 TkJg^TifflaLt ^ 5 7 Hl^lffitti H t U * 5ft, L^L*--"'^* 4 x i<r*mol/effim-f2>t.mfr\-<d*:s *-»««#;«*-"*- Ce# i>.»49*-ctt*a*^? 7 URiliO^fflUtt^nrtET***'. 1 %NaHCC- 3 *^^T 80 C it*k#^. *** y ^- ^esmwiusn, 1 x io- i moi/ iiji± >^-^mmm-cif±em Table 1. 2 & & ^HFig. 1.1 i) BJ <b #» 5 K, *-A^jftgtfsjg < tiffh^. * * *-y ^- feiakftiftij^tfszki < * &#. &ftkffl ffi?l-cwbti2>s'y 7 h*&{ < ^ f t^s,, #> ib *-;v:^ if$i#f'3-x!2;ifc5$i tt*7 -^-fcjfc^t/hsl^tfs, AA75 7 h *U -*-f±a A. 7k &&#EfC$JiL, *-^^tt7kfcs»^i) T, ^7 7hi@g-e*- -^fi^itf's (cjia L t i^a i #*. <bns 0 3 :*«ltf S^^tr}iTable 1.1 fc&^l/cj: 5 rc***y -7-!Kft-J-.z,fi-g-W$IJ#/* fite - 5 -

12 Table 1.2 Effect of Mohr's salt on the grafting of acrylic acid onto fib~r. polyester fiber. AA/H 0-6/4, dose rate 3.2 X 10 5 rad/h, irrad. temp. 24 C I Fe(NH 耳 目 4) )~(SO 2(S0,) 4) 2 Irrad. time Apparent graft, Z App earance of solution mol/1 ta D» E 3 ) aft er irradiation Rigid gel ti _ 4 X 10"* Soft gel tl " tl II 2 _ ;3~ 30.8 呈 1 X 10" Soft gel » 11 2 ii. _ 4 X'.io" CI ear solution tl Viscous solution II Soft vel 2.1 Clear solution ti 25.0 it 3S.2 n _. -_!, 0.2 Clear solution 4 X it 3.1 " " " 11.34, ~ ru) 6.2 Clear solution mo 1 i 17.8 II II ) Sacurated solution 2) After extraction with boiling water. 3) After extraction with 1 X NaHCO aqueous aqu~ous solution. Fig Irradiation time(h) Effect of Mohr's salt on the grafting of acrylic acid onto polyester fiber in 60 vol* aqueous solution at a dose rate of 3.2 x 10 5 rad/h at 24 C. Concentration of,~ ~ ~n-3 Mohr's salt: (x) 1 X 10~ 3 mol/1, ( ) 4 X 10-3 mol/1, (o) 10-~ 1 X 10" 2 mol/1, (A) 10-~ 4 X 10" 2 mol/1 (saturated soln.) (A) 1 X 10 _ 1 mol/1 (saturated soln.). 戸 ~

13 JAEBI-M 9481 nkk. Effi<Dmm-c*>2>mm.m, im m&~c >2>i&i\:m m%mimiftm&<daa?-7y hm&k%t-tz>-m'&%]lfflmiia<d%)mz-t:fl?tifig.l.2, Fig. 1.3 Kf^-fo PitiOm^^M kl.±<d = m<d&.&rvmi& 3. 2 x 10 5 rad/h, JllitBIF.fl 3 m$vcii-1r5h fyfrlr} 7? 7 b %>t&mi&wkm<dm&%fi g.i.4 KTii-fo z-ommai), AA m&vcft-f%>wmih$ktt. CuC^> CuS0 4 >*-JfJ /[BJ?T&.5 t&t>fr&, ^ g±ttj:j>, Cixtca-g-^ihffl '?. *-^4SfflLt, felt *lft-cfcl:*-*** Irradiation time(h) Fig. 1.2 Effect of cupric sulfate on the grafting of acrylic acid onto polyester fiber in 60 vol% aqueous solution at a dose rate of 3.2 X 10 5 rad/h at 22 C. concentration of cupric sulfate: (+) 4 X 10-~ -4 mol/1, (x) 1 X 10" 3 mol/1, ( ) 4 X 10" 3 mol/1, (o) 1 X 10" 2 mol/1, (A) 4 X 10~ 2 mol/1, (A) 1 x 10" 1 mol/

14 JAEEI-M Irradiation time(h) Fig. 1.3 Effect of cuprous chloride on the grafting of acrylic acid onto polyester fiber in 60 vols aqueous solution at a dose rate of 3.2 X 10 5 rad/h at 22 C. Concentration of cuprous chloride: (x) 4 X 10~ 4 inol/1, ( ) ~ 1.6 X 10~ 3 mol/1, (A) 1.6 X 10" 2 mol/1, (A) 4 X 10" 2 mol/l ~ Mohr's salt «20h ft Sf < 10-0 io " 2 [M](mol/0 FeCl, A-l i itla 10 ri Fig..1.4 Effect of copper and iron salts on the grafting of acrylic acid onto polyester fiber in 60 vol* aqueous solution at the dose rate of 3.2 X 10 5 rad/h at 24 C. Irradiation time: 3h.

15 JAERI-M *s-*-mm<d&w ~ち( 容 量 ) 以 上 では,モール 塩 が 添 加 してある K もかかわらず,ホモ 重 合 速 度 が 大 き Table 1.3 Grafting of acrylic acid onto polyester fiber in the presence of Hohr~s Mohr's alt. salt. Effect of AA/HjO ~f ratio of 田 monomer solution. ssl~ Concentration of Mbhr's salt 4 X 10 _3 mol/l, dose rate 3.2 X 10 5 rad/h, irrad. temp. 25"C Irrad. tine Apparent graft, Z Appearance of tolutlon by vol. h after Irradiation 9/ Soft (el Rigid gel H 8/ Soft gel Rigid gel t* / Clear solution Viscous solution Soft gel 6/ Clear solution Viscous solution it / Clear solution Viscous solution " 4/ Clear solution Viscous solution ii 3/ Viscous solution 2 ir Soft gel 2/ Viscous solution » Soft gel 1/ Clear solution Viscous solution II 1) After extraction with boiling water. 2) After extraction with 1 Z NaHCO, aqueoua solution.

16 JAERI-M 9481 a 3 mxmo&w rmf&%<d%>&<dmmm &mzfig. 1.5 nc^-t. 'tth.*ito t<d &, 8i*) SUBffl**i^s, ~ 更 潰 法 を 祭 用 出 来 ないか, MttfcjErrftffctflBrc-J-ayfcttrc. 漫 演 法 rc 近 づけた 状 態 K するため rc. 繊 ««fc 維 K *y *-m%20q&m mji & %. mmmmmtkmttiito ^^*Tabie 1.4, Fi g. 1.6(C^-t 0 Table 1.4 CC*3tt S, 5 K, TA- * >fflffifc & ^ 7 7 b *0«iXi. r $ %T<ri, Mtmftmv^jtibitc&MBzmftmfr<, mmnuo^m<dmxn-k^m^z><dx. V. d. G. m^-m<omtm0.5rv : 0.17MTad/'6ecld J ttl^:tl. 1.8 X 10 9 R^6.6 X 10 9 nw.-?* v h-taifig.i.7 #s^s.^77 n-&ar«, m wmt m*$mt&% ti Cilii). fyfrtf<d7y 7 hs-a-jik«6. 5 x I0 3^b 1. 8 x lo 9 i:s5 0.75*fCJfcPW-* Wjjfef^fbnA, rad/hoii4$ gh-cib * 40 <d t< M S 30 0) M OS a 20 < 3.2X10 i rad/h 3.8X10«rad/h 10 J i I 0 5* Irradiation time(h) Pig. 1.5 Grafting of acrylic acid onto polyester fiber in 60 vol% aqueous solution containing 4 X 10~ 3 mol/1 Mohr's salt at different dose rates at 18 C. -10-:

17 JAERI-M Table 1, U Grafting of acrylic acid onto polyester fiber in the presence of Hoar's salt.. (Impregnation method) AA/HjO = 6/4, Concentration of Mohr'a salt 4.0 x 10 -^ aol/1, Van de Graaff 1.5 MeV, irradiation temp. 16 C. I. 0.5 Mrad/s (1.8 x 10 9 rad/h) Pick up, % Dose Apparent graft, % D/C Apparent Mr ad X 100 graft, % 2 D C» > E3> I vn II Mrad/s (0.6 x 10 rad/h) :3* ) Without water-extraction..~tter 2).After extraction with boiling water. 3) After extraction with 1 % KaHCO, aqueous solution ^

18 JAERI-M Mrad/sec 0.17Mrad/sec Irradiation time (sec) Fig. 1.6 Grafting of acrylic acid onto polyester fiber in 60 vol% aqueous solution containing 4 X 10~ 3 mol/1 Mohr's salt with electron beames from Van de Graaff accelerater at the dose rate of 0.17 Mrad/sec and 0.5 Mrad/sec at 16 C. ~ * 10 s lo e Dose rate(rad/h) 10* Fig. 1.7 Influence of dose rate on the grafting of acrylic acid onto polyester fiber in 60 vol* aqueous solution containing Mohr's salt of 4 X 10~ 3 ntol/1 at 18 C. -12-

19 JAERI-M m%mm &* tt4 X l(t 3 mol/&, m*&&3. 8 X 10 4 rad/h T o fhfeisssfc Fig. 1.8 (^"to 40 C& 5 0 \2^k±-rnmmmtHttA,iiM.bti-r, *>h?y y t-m-zfy y hs-g-sett'hs < 4&<, Fig. i.9## (,«, tni ^ #e>fta ^/^ fis-ffc^ *-*-**-«. lsnottao kcal/mol, 5 0~9 Ot T 1.4 kc» I/mo I T i3, ~: iligf2 42t T^fr&o ~ち 附 近 を 境 κ グラフト 重 合 速 度 が 大 きくなる 傾 向 がみられる 照 射 温 度 各 温 度 K お ける,グラフト 率 5~ち rc ;t'けるグラフト 重 合 速 度 をアレーニクスプロットすると *#^?lifct, 5 0t«±i4 0t&TTO*»O«Jt. X. BKtf«H<4*S. JtL# J /? n ^#/h3 (isottftci 9K5 *.ibnj: 5. PET0^5^effiIfl8 oti is-c^so AAttPET ^figp^-fcsal. #y*m um*i&tts- Z>&&%!>?-?: >?> i^fts, #7^fe» E&TTtt*./^- «Mifl^ ffiifciie:^3^7fci&. #J#3 ^7 7 hs -jse«'h3<4a. L^L^^iP'ari-a-L^^'J AAtti-g-jgE^fi^e^-^fttt* g <, PET»fiO*f)*^^, *&l^tt*'; A &m-fc<dfrb& ^ft-k$ < 4!?. fflffis #;fij#, g#go-t < T, ifs&*%m*fivzk&mjk*ir>j!> i. m&&3ktt±iz<dm&-c. «WBK*«fi<448. S7«^7 7 H#aBCtt/hS<4S^. SU*^?? b* l*& < 4& W4 ot&t m%um^&bn&mmmk!gst)nzwfflk)ti-r2>3sm%-r2>±*t)k. s -a-f ^«^* SE*3E^x, fi?.li^hlc)i*f-ta^7 7 h ^ t^^-&^ Be^* ib^fco 2l 9lilKi-!o-rttPET«ti(iO. 2 g*15ml *7-7-}?S(CggtLT r *J!fUM*fT4 ^7fc S*4 1 5#^7 7 * x = Lfc*B<&. *#g*-c&i!sbi l*8fejil.1, 10-5 mmi% Sff.K 4-4T3S# ^,4Bfc*Lfc*'a-0*;&»tf- ^7 7 l-ag H8l<fB#IS B8#* Fig VCTFL ito M&mk±. Bet-t&iSifcf ft *# & K7 7 h ft(csc«l t, ^ft^l^oaat^, -*fcta,km%>-$- fcw., 7 0 t T 2 0«JEJft«L. S*»JS Lfc** * 'J *- * D & SLA. Fig.1.10 *?,?9^4X 9fc. 3 OtOHRWTtt. B-JHIi^M-ClfcKri-Si. * ffifpfigw *^. ^fmfcffcbb^, Kl^*^(t ^7 7 l-sg##(b*is#. SNHHi*43 #. mmfto***4tk&^ttt Fig.l.n K^btiixmc, n&mmti.mm< m% LtibOZ-kfrb. 3 0t!(D*«^7 7 * &- tfcfrbti2>m&$mt. A A* 7-* - * Ja PETI*3lH5'^0ffi»J» s. fyfrift?? 7> JS4 ieltv^at tkj it4 4 0i*t btlso 5 0 t g5b«fflawlc*'^a^^»t ^7 7 hkjskil^sbislfrft&slhtfsft,^ -13-

20 JAEBI-M ~t " Irradiation time(h) Fig. 1.8 Effect of irradiation temperature on the grafting of acrylic acid onto polyester fiber in 60 vol% aqueous solution containing Mohr's salt of 4 X 10" mol/1 at a dose rate of 3.8 X 10 rad/h. ~ l/rxio* Fig. 1.9 Arrhenius plots for the apparent grafting rate of acrylic acid in the presence of Mohr's salt. 14-

21 JABRI-M «J M V. 20 CD u at 10 (30*C, under vac. -srs 50*C,N2flush, 15min Irradiation time(h) Fig Grafting of acrylic acid onto polyester fiber in 60 vol% aqueous solution containing Mohr's salt of 4 X 10~ 3 mol/1 at a dose rate of 3.8 X 10 4 rad/h. ' (A) flushed with N 2, irradiated at 30 C, (A) un~er degassed under vacuum, irradiated at 30 C, (o) ~ith flushed \*ith N 2 / irradiated at 50 C. j i_ Irradiation time(h) Fig Radiation polymerization of acrylic acid in the presence of polyester fiber and Mohr's salt. 0.2g of fiber and 15 ml of monomer solution. Conditions and symbols are the same as in Fig

22 JAERI-M r^ y»m7kmm<dtitmmn'&krii- -t*:-»t&ffito<d%}jik JHSTT2 6 CT«li^3.8X 10*rad/h r» ]#.& L tff oft M*ftTTtt, *-»1&<Dffimft1 VJ&<&l(., 6 :9fa! HS&tT *** - 'J -* -f± i>* *->>- x -* ( 20 : 80) ^T'^tC>BfLt%^jga5* ^Sf± gj6t 5 n4^o3fe. Sfc-e-^iiOfetraKJ: t>. S-&&K «*» # ) l/8k&tlx^2> 0 SbKaBt^Stiti^iOfiTTia. #^1:«* -^ gsaqftj: H.0~4.3X10 6 *tjl.5~1.8x10 5 it?j:f l/20(c{ TU-t^& Dainton^fiT^ 'J ^-T $ K 7k««r i» S^fC*"** & Cu 2+, F e 2 + #PflJ MM Sf 5g u. J5Scfi7^*^ ^fit.sfe;75 :^j *5 : -^^ fiiijj^ «^-#iirrj: 0 rjgc&c.i*^u^0 Huglin^'^fi^-f ysoaa r i^?7h^ki^t, Fe 2+, Fe +, Cu Z+ <DM^9P LX^iCtimb^fCi,. &jk<dmmi&mlx\r>2> 0 Z.nb<D%Z.Z%mKAti2>. *-A- &A A S-&K*^Tf?juiSJSK:H-5L, fl-^jt gflti R)B $l*t^7 7 H^Ki^tH, *-^ts «ilirt'x SStScjSK35 5; e>"'- *n ;t,~いては,モール 主 主 の 繊 維 内 への 拡 散 速 度 がモノマーのそれ <Dfyfrn<D7? y bfi-&k*flth:w1m«i**53 ^trtt4^o IS = x *-»t *mvt 2> c *c «fc b, flmifl. ***? y * - $* WML. ^77 h ««** & t tf!f»rffift ;5*>*j-T ある そしてとのととは,モール 塩 以 外 I'CAA のホモ 重 合 の 抑 制 ~I'C 効 果 のあった E 価 の 鉄 塩, ^n/>4*»ft, mmft-v%n& &&!>. ^<mm^<d^-x^yy n-g-srgc^-a-atitt ~:~:~:_~f_m~~~'s~~~~t_~~_t~e~~~~!~:~~~~p~~~:~~~~~~o~_~~_:~~~~~c.!~!d Table 1.5 Effect of Mohr's sf»lt on the radiation polymerization of acrylic acid AA/water = 6/4, dose rate 3.2x10 rad/h Irradiation temperature 18 C Concn. of Mohr's alt Irradiation time Total conv. H rnol/h min. % x10 s x10' _»> x 10" x10 s it xl0 s a) Hater insoluble gel was formed Polymerization was carried out under reduced pressure of 1x10" 5 mmhg. -16-

23 JAERI-M m&ozt oi&mmimz., %-r, -o ^f <. *-*m.me&m%.<dmmk a, ^ttidpetii-naat/?y t--t PET«-MO*y ^- ffitfc^^afclt m.m-xr^bmt <?? y \-n^-t >itmt±m-k^^t-th^mmmnncn-thp ETmm<ommm.±m-<±o Table 1.6 tt 20 C M* 30 t (C^f^S g«^flbj 1 HSFHTS: b ff?c 24^^ ^-& ^PK*^-to Table 1.6KBX, 25 C fc*.^2,«fl^sslj S*R' < 7 ^ - * - 17) % 15SR L 7fc 0 PET 5 «io.7 17) T** 0 &mikm.ik-km-t: 8 ft $ ~ i o & tti ^Ji*iH1 *-*#, ao&t % «:Ufaf #'h3(/-><, -^ ^ n^i^t^tiisoma^tti^n a4, 9.3t?.5#, liltii 'h ^o ty^*7*3-*, i?^***47«k# 8 it 1 2T >S#Jjgf3fttt#»4 0*; Table 1.6 Swelling of polyester fiber in various liquids Liquid B.p. Degree of swelling < at follow- 6 (Cal/ ing temperature and time. % c c )l/2 20 C, 20"C, 30 C, 30 C, lhr 24hr lhr 24hr Methylene chloride Chloroform Carbon tetrachloride Ethylidene dichloride Ethylene dichloride ,1,1-Trichloroethane ,1,2-Trichloroethane ,1,1,2-Tetrachloroethane ,1,2,2-Tetrachloroethane Pentachloro ethane cis-1,2-dichloroethylene trana-1,2-dichloroethylene Trichloroethylene ,1,2,2-Tetrachloroethylene n-propyl chloride iso-propyl chloride n-butyl chloride Mono-chlorobenzene O-Dichlorobenzene Benzyl alcohol Dimethylformamide Dimethyl sulfoxide Nitrobenzene Formic acid Acrylic acid

24 JAERI-M 9481 fctcztibommm**; -*--mmcmz.xmui?s7 y *m^zfiik^fto Table 1.7 set gsjp L±mm^m^±^^o^^ ** *-. -<v ^A-T^a-A-, 4?^^A-*A.AT«K^ ^^'ftj^'ft7k^^^ PET»Pffl(l^ EK*»^a^5 7 >>Km&fem-th tcrs.ta, %}&**-&fov±t>i, PETKtt-t&mm&o Table 1.7 <D%MB%iK.i). ** # 'J» - $#/><, ^^S^fMTig^^? 7 h ^ft Table 1.7 Grafting of acrylic acid onto polyester fiber in aqueous solution of acrylic acid containing various liquid. Monomer mixture: 60 % AA aqueous solution (containing 4xlO~ 10 J mol/fc 3 工 /~ Mohr's salt) : solvent = 10 : 1, by volume. Dose rate 3.2x10 5 rad/h, irrad. temp. 22 C. Name of solvent Apparent graft at following irradiation time, % 10 min. 25 rain. 60 min. Hone Methylene chloride Chloroform Carbon tetrachloride Ethylidene chloride 19.S Ethylene dichloride ,1,1-Trichloroethane ) 1,1,2-Trichloroethane ) 1,1,1,2-Tetrachloroethane ) 1,1,2,2-Tetrachloroethane ) Pentachloroethane ) cis-1,2-dichloroethylene trans-1,2-dichloroethylene Trichloroethylene ,1,2,2-Tetrachloroethylene ) n-propyl chloride iso-propyl chloride n-butyl chloride ) Mono-chlorobenzene ) ) o-dichlorobenzene ) ) Benzyl alcohol Dimethyiformamide Dimethyl sulfoxide Nitrobenzene Formic acid } Large amount of poly acrylic- acid was formed in liquid phase outside of fiber. -18-

25 JAEBI-M m & V>&&&&?$>& ft, -gfv. d. G.iP^Isi!? m :?-ig ffl^& * * && So *-*-*,»&$, mft%-m%i:. Fe z+. cu 2+, cu + ^SB(cii). «t*t^g&t m-a-s wmo&s&rv. $*&. mi&&tt w* '&mi&, -t<dtiz<d'mftmv>bn&n&%ikm!t * ^m&iwm-t2>%imi&*7!>>*±o m&. «* &$»»# :*: sa. Fe <c u <cu + jp-trfe o^ 0 c 7k?gts MrB(ci,>^t, */ *-mm &9t&±% <. *-**» # 4 * io~ 3 ~ 拶 以 下 ではほとんどグラフト 反 応 は 起 とらず. ~ち 以 上 moi/0 ではモ -^^(rc ( C-5*'ea^ Wftfl^** s 3b*trtt435»ofe <1 *:g5fl- 5g *fc):* *S3 &fc>n& * ~ 拶 を 用 いた W>W/7 7 h ^ 5 0 fcfc^ a ^? 7 I* Jt-&jilE(C&J -t$sf:^ J #3rIli'-<7t, > 4 2*C p&s*«8(c^?7 h^-m*t^kffl» ^was'fkl. 4 ~ 彰,,"C ;J:,"けるグラフト o cy.t-zttmmfflftfrbnftft, 重 合 速 度 より 求 め 5 o 'Cfei±trtt^bn73:^o7t ^t^<d-y yy H5*rcws/7 7 n^-ski i>* > ±%-fr<r? fe&fcx-**'#-llt "Ct8.0 kcal/mol, 5 0 ~ 9 OtT 1.4 kcal/ mo 1 "C < > -= 7t O ^-^ gsflnkt, A Afi< JiK * fe:f. 4i«K'J'-Ol^t*ifKiT3*St tiifc>frofto 77? VM^i^UT^mii <fhl 5±V>K, m * P E T <DBMmc-?\r>xm%i L Tfeo % *ftkft**&fl PET fc«ffltt3fita*tt;&^?7 M-frfciEji^aoiefci,*, #!* -19-

26 JAEBI-M # V 3-7,7-)VmB.^-<D***\! 'St tf77 hsb" i. IB m 7 7 h a-g-s-fs*, MMtfl. * * * y *-<D.&%&>wi-tz±it> mi& j t>mm. FET ^$S Mt LtozL&tt,**- v>*mz.it* s-*-7kmw.%m^2>z.ti{cil<9. nmkfiy y \-n& ^ttttl^fttlwttl. 7 fi y *m<dtik%imfiy y t-m Wfft m% tlx, 7 fi y />-$*/-* - HMfil^t^^ ^'J*i (MAA) Jfc«ig^7 7 M^t^^-^o PETli-MlPMAAO/77 t-m&k^in-ztt., -=<Dm% m ' nie) ft&z>7!> 1. iiltt BSWft^J:* *> T& i?, ^^MMSKJ:S^^^^KC^^x^'S^n^^ ttf1:c!:^i'^^^ MAAttAAt^Kft^gMKJ: o t l ^ ^ t D^<, tftf^*k»ltmi < 88^RB#Jl0tfKJ:&flIJUNIlK^^T «-<. Si^5 7hfKosirc5^-?:fi, r^ y *<wfi7 7 h mm t a*tn3 m-at^ & 2. H«^>* MA A* 7 v-tt«j ETfC fll7fe% tffllajfe 0 i^ftliltffll/^ i ftx^v>-«7lj mwm&i mm, SL±%oxi)&o ***y^- ^B8«r«isy^a7fctoK^spL7tsEKffitt l&js4s«i& *-tot tffl ^A. AMBU^fl^^ffitt^ *!? T*& PETi«)0.2g^Slcm M^fKAn, M fcan/t. a^t?^* 2fl-HaD^^(t:«^L?t. &u (i9±2t!) K-^.%^±mcmm<DU KT f0 co, 2000oi $<DrffiZMMLtzo mmmmmzmml, t ±x-ft&m&l. &.& ^.MitmmL, Jtfiifftl* & vz&frtfofiy y t-mt Lfc ftijciffiloitobmaa* y?-&&* ]?#*{ <jgjs-t&tf»fc-c2>.&. ^ ^ /fcfekc, AAO^?7H^O^ * $><Dk($bA, t>b%\s>frfrtt<dfi77 b ^&#7t t7t^7 7 H^SfK4SfJMAA***, 'J -*-i: &5gtt& J: 5 CCLTfr* ojfc fi «a****fflltil^n:*%^««!>(c. IMJPETli^fet-^-uWL, ST K7 7 b cf"t*5js *7^-7j; lb >'fc7jc ^f 3-, tft*7 0 C It SCC ; ;,, 3 T?S T, * =e * y f-*kslw>(t<d;77 i- m*$u6.!! J> ***-y ^- *4*5EL -2 0-

27 JAEEI-M t. n^ir yy httitttftftft. -to wis **«* * ^xmrnl-tt*, S?>KIIAAO 7 MR mir-y V9*&, 1)n>vv AjatcLtRffittftfflJgL/fco Na, Ca -v. E&«:- -;ft-? I ;ft fi^se^ mn, g^#^-7 ^01 %s ** &(«: ^7 7 naygfcgjfl, 8 oqx:2mffl (a) 3.1 * * * y n>m.7kmw.k & h r y y t M-& R$ H«g J # &ISL. ^yyr-wlmmslm-ti.tammx:t>^±o^im-cml±.^k. AA s-?y> w.-sk&'^xitt,.mft<d**n *nmlxpifti[cfy 7 tm&zmfiz-itzit&k. & $>mfe<dw;1)bft>h$hx' >-=>± 0 $>x"& iffiom&tiiffitdmtmftfy y tm& >Mftt* : VC.i>~ける 重 合 禁 止 効 果 を 調 べた en &<DfflM<D'< y ^^ ^TSfcJSST&ofto ZZX'AA?? y h S-a-OBgfcteJB Lft Effi m.m *-A<m, nm m^ mmm±m.±irrx, MAAtc^wi^itM^w^*.?r «g*, AAfcftLT*$T&oft*-.n,EttMAArcftLTtt$tf8 **#U ^- $ t- &&$!«> fcttfsffisfcfto ^c.tfe!.t flifetfi, mmmzffitinlit * ^ -*--jg& JBlo ft. ~ 彰 水 務 液 を 用 いて. 添 加 する 硫 酸 銅 の 漉 度 のグラフト 重 合 κ 及 ぼ Table 2.1 (CMA A 2 OJBTMgffc&JSl/Vt:. fet/trt S»iE^ «^7 7 hs^fcxs す 影 響 を 調 べた 結 果 を 示 ナ 念.i>~ &m& MKmz.2>u@itix 7 5 c gaft 0 «t««!*«badl*u>*>'»-*»«?«:* : *** 'J-* -# [ L, :gb flfl ts#fcj: ^>T %?yy t-mmit i?ffi-* t ttg*8=t& => ft, fc$ l i.oxio _3 moi^ «gtt^ja-^a<t. ^? 7 h ^ (.B.mL±&*y*-m. K%-fh3).frn ryy hs-a-lft*^^-* *!)-^ ) ~ 39.5«T^^^ ^7 修 でみかけのグラフト 7 h^fc 53.6 率 は * % *5#f,nft 0 iiik^ aik*ltap-t-si, 3*frirt?y 7 h^ttfaiai"js^-ts : t-fclk**:#v -*- &.l$.t±ft.mirc4>< 75: j?, 5.1 xio~ 2 njol,/0 T fy 7 h ^^fi OO~ loosgk: 彰 K <gjib3ftft#lif'c So J:OJ:5KLT#WAMAA/77 htt«tt«tiiw«>s*«ft <. mmmtnm ^^t> (b) *y-««?# m&tm^ s x io" 2 moi/^^snlfts-6-?r5rffl^'tmaai7j< ifieifc*^^.t:5ljrufti^ ^* Fig.2.1 Vcm-fa (.mut)k*?^x$i%n^r?y >m*mbnx\^2>&, %k%n%ni*jz* <tsi2o~9o -2 1-

28 JAERI-M ~ 拶 モノマー 水 浴 液 では, 液 相 rc ホモポリマーを 生 成 す i>m<dmammlx %?y7 H ^ ^ C b-i*. 5 0 ~6 0 #.fell */ '-lltffift Table 2.1. Effect of copper sulfate on the grafting of methacrylic acid onto polyester fibers (1) ~ixture: Monomer.mixture: 20% aguous solution of methacrylic cry1i~ acid, by vol., 0.2 g of fibers in 5 ml of monomer mixture; Irradiation, 3.6x10" rad/h., 2 h., 75 C. Concn. of CuS0^5H 2 0 mol/a 1.0 x 10" x 10" x 10" x 10~ x 10" 1 Apparent graft % a) Total conversion convers~on % Graft efficiency % Very high Fib~rs a) Fibers could not be separated from gelled homopolymer 50 [Cu*]=5x10' 2 mol/l 3.6 x 10* rad/h C. Monomer concn., vol. % Fig. 2.1 Effect of monomer concentration on the grafting of methacrylic acid onto polyester fibers at 3.6X10* rad/h at 75 C. Concn. of copper sulfate in monomer solution, 5X10" 2 mol/

29 JAERI-M (c) /5 7h$KSIittSIiilSOM m%mm* 2 0 C 1? 150t!tT3E<k^-dr. ^5 7 hs-g-oflk^ft^^tfeo SSI**!** Fig.2.2tCwi- 0 MIBKI 9-4 otrtt, RUBBSH 3«FH-*T^7 7! «fit A. '*>- bh.fr v± 5 0tTtt3«FW S8JW SI 4«W*tt«)/77 t-^#ftbft/t 0 6 StJ-feLfcTttfiK** *bn, RgJH^Fiaoiiiai^tcfaraTfB^?? hjefcai-t-a s^at**^-. fis*=tsk35 j w< * Spoilt8)$^7 7 hs & <; : #, &L <yh?yy h$hrirttl, 120t y.± K*tiggrtt. tut^^?? \-mti.mbtut**<=it 0 -titt>*>. PET *^6» SK. * > 7 5 t! *"*»'&> L.7taK«:t*-e. fry \-H&fr*.i>1imKi?Z.2>Z.ft> i t>fr2>a AAO*^(CH4 0 ~5 0 td ftfi ak#**>*;f!lt *=>/&#. tfthm A A A A # 'J * ^7-^««i(i:s*f-i-a gistt a^(cj:a i<dt&frtih 0 MA A 3 O 'crci-^arfy *^-r ^KSsfi-aUgfHKtt ~ちであるが"7クりル 1 *-C*a*s. T^U *Kfi 酸 は 6-7% 6 ~7*T*So である とのため toatomaafct, は. PET ttftksalkx <. PET *7^l5»aK-4THB«iaR*«<tJtiM»T*S#, AAttSS-Cb^* j) PETF*9Si5fCSA-t& T, P ET # 7 *< #MK*l&T3-, Jfcgt ftll loak-c%*«i(c^7 7 hrje#aitr4 fi:bft.&. fis»fik«r*<-*-<2> ^7 7 h ^ #( T:f S tt. S-& j@eiot^ PET-=r h!> -y f*<dfe9lfri&<1i!), y*ij ^R$C Wiig'a' #^^**-jr--6 3fcJ6T*a #^.ibns. PETic*hf * * ^^1-7^*75 MAA 20 X aq. [Cu*)-5x10"*mol /I 3.6x10 4 rad/h * 50 Irradiation time, h 100*C 50*C --' ~.1 4J20.13$,150*C 印 -C I Fig. 2,2 Grafting of methacylic acid onto polyester fibers at 3.6X10 4 rad/h at different temperatures. Monomer mixture, 20% aqueous solution of methacrylic acid containing copper sulfate, SX10-2 mol/ ド 混 合 モノマーの 水 海 軍 液 のグラフト. 合 に 恥 いて 問 機 の 現 象 か 報 告 されてい i~) ~ & 40

30 JAERl-M Fig.2.2 >m.tk^m<0 log-log 7'n t-fcfig.2.3 JC^-f. rfl«:jfc^:t*^(9 il K«fftS»pJSSft**^-t#«-C*S. fl&&sk C *EHTtt/3 = TI5K 100 : MAAZ0%aq. 50 L [Cu*]«5xlO"! mol /I - 3.6xf0 4 rad/h ~ 0.1, -! 1 I I I I III 0* 2.0^2.1 for the grafting at temp, of 6S«$S?> I I 1_1_JLUJ. ' JO Irradiation time, h Fig. 2.3 Log-log plot of the grafting curves shown in Fig (d)?? 7 * thmttt-tz>m.%ium.<d&m js&ut* 7.2 x lo'r.dfc-sglx. mmum.* 2 oci t> i2o c a-zmil-z. ^??n * Table 2.2 KTS^O -24-

31 JAERI-M 9481 Table 2.2 Graft-and homo-polymerization of methacrylic acid in the presence of copper sulfate (1) Monomer mixture: 20% aqueous solution of methacrylic acid containing 5xl0~ 2 mol/jl; copper sulfate, Irradiations 3.6x10* rad/h., 2 h. Irradiation Apparent graft Total Graft temperature conversion efficiency C % % % ~ 彰 であ 9. 照 射 湿 度 の 上 昇 と 共 κ 大 きく 念 り 7 fit 47.1 %hh.\). mftimmft bkm<l3:2>tft.%kwi.'>l, 120 C-Ctt.f?y \-mtz096t 'tfj -f?7 7 b«ilih:i00^tl>o^ 50t!i bmwl-cti.wifton&b.&tt.tgikkm jklxft&m^fy 7 h*4#sci34iffi*7t AA7k«^*ffl^&^7 7 b I^TH. frffi K&ZZ**n&*%&Kmi-t2>Z.ttt M-C&-3fcft, MA A «-a-(±^^tai3. C (e) $**»# **Fig.2.4r<:*-t i~. 0 «<frttmftt s?itl>!), flr#jr?w#«<*«i gttk**a. ««**# Ol4log-log7'B-y ht4ifig.2.5^?)ftsa fisgg 5# *l!^ 0 tt 2. 0 T. 'flttt»***ft'ffclttflfx ffitio*. Fig. 2.4 * *!>, S-a-S3«^7 7 H^Ett/? 7 b m6hmzk#k.mxt&#, i ^5 7 b $K>W/7 7 b S-S-aE* i^ff. ^ibs^jc*-^* ^5 7 b &<&&&* 'ibtt-taci!6 5 ffl*4o Fig. 2.6 /!&(! ^3 7 h$5*tt(ti^ ~ 桜 Kぉ けるグラフト 77 b S &C i l:$ 重 合 速 度 を 線 量 率 K^lt 7-a. h L7fcfc -es>s -25-

32 JAEKI-M i 30 on I o / /T / / <"> S-exltf^O O 1.9x10" rad/h.6.5xio s rada ^.BxlO'rad/h * MAA 50%aq. fefl- 5x10* mol/l 75'C. i i i I S 6 Irradiation time, h a e Oft I luw r MAA 20 X ag {Cu*)-5xMriiiol/l 75 *C. 0.5, ' x10* rad/h 1.9xl0*rad/h 6.5x10* r»d/h 4.6x10* rad/h _i i i I i I 2 5 Irradiation time, h 10 Fig. 2.4 Fig. 2.5 Grafting of methacrylic acid onto polyester fibers Log-log plot of the grafting at 75 C at different dose rates. curves shown in Fig Monomer mixture, 20% aqueous solution of methacrylic acid containing copper sulfate, 5X10~2 mol/l. * S 50 [Cu*]-5xl0~! mol/l Fig. 2.6 tn 13 1 a-0.55 MAA 20% aq, aq. 75'C. MAAtCHjCt),^) 20 % Bq,19'C. 10' 10* Dose rate, red/ht. Effect of dose rate on the grafting rate of methacrylic acid onto polyester fiber. ( ) 20% aqueous solution of MAA, irradiated at 75 C; (o) MAA:(CH 2 CI) 2! Water=12:8:80, by vol. irradiated at 19 C. -26-

33 JAERI-M m^*v~s*mn\^it-m.mm il'hiry7 *-&% tt-c, AA ^7 7 hs^k^tf&filiu {JZ^-ffcx*-!^*^-?, S0fi»J L T MAA > if ^ 'J A-gf + -^'ft*^^>'i7k iffi.e!cjt* 2 : 8 (SgiSJfc )K«oX. ^ * ^ 'J ^SS -ffi-fb^^^xdilj^^geax 2 Ot!-Cll»L±iie*ftTabIe 2. 3 (^"to Table 2.3 Effect of ratin of methacrylic acid to ethylene dichloride on grafting MM I: (CH C1) Irradiation time, h 2 2 by vol : 9 App. graft, « Total ccnv. % : 8 App. graft, % Total conv. % : 6 App. graft. % Total conv. % : 5 App. graft, % ,. Total conv. % : 4 App. graft, % Total conv. % : 3 App. graft. % Total conv. % : 2 App. graft, % Total conv. % : 1 App. graft. % Total conv. % : 0 App. graft. % 0 0 Total conv. % 21.5 Monomer mixture: 20% aqueous solution of MAA- (CH 2 C1) 2 containing 5 x 10~ 2 mol/jt; copper sulfate Irradiation: 1.6 x 10 5 rad/h., 20 C -27-

34 JAEEI-M yn!( l&b1mzfroit 0 i ik*?-i<'>'%wimi~2>t fyy I- ^a^%hhi> Jt 5 KH. \>, * * * y *m : ~^t;x^^voiabgi±;^6 : 4 T**> ^7 7 (b) mmmmm &m va^^u^^k^z-ho * * t V»&--i <fk*3-i'>-lk<d&&tkfi i l 2:8180 (S=8Ut ) S-&$i fflu~., -&»ih#j<!:lt 5fcaei8»K*^;i.T:, 3 0 "Ct r $*M*f L jfc**y :$5: Table 24 Table 2.4 Effect of copper sulfate on the grafting of methacrylic acid onto polyester fibers (2) Monomer mixture, MAA: <CH 2 C1) 2 : Water -12 : 8 : 80 by vol., Irradiation, 10~ 3.6x10* rad/h., 2 h., 30"C. Concn. of Apparent graft Total Graft CuSOf5H 2 0 conversion efficiency mol/jt t % % x 10" x 10" x 10'* x x 10"* mwtm^r i.o x ICT I/ß 2 mo\/ mija-t2>t 添 加 するとグラアト si? 率 はy 11-12~ b^fiii 彰 ~ のほぼ 12% 一 <Dmt ^.<Dmc±-x:mifyy tzhmkimmmomnkdmjztmcmx-t&o mmta* 定 の 値 κ まで 増 大 し, loxio^moi/et-cm^h と.グラフト t,?? y h 率 $«5. は 5.H 4,%%<&T-thft, 彰 κ 低 下 するか,グラフト fy y \- mtt 効 率 は 100~ ioo& 彰 となる t 4i, 以 kkt<dmm-ck±. 下 の 実 験 では, 二 塩 f& Yti^i^^s^^L*^* ;-*-m&&<dtbi&tfflmc 5.i x io- s moi/g<d.mzm^± a (c) 7?y h$k^f5lwso*i m%u%.* ±ifn 3oC, 4 oxiirc-t&t. ryy t-bl&ttsbkmz. tj^< & S-S-ffiffii tts^ffl *«-*. 50tK44 t. «t»»caj«8^?7 H*IKttJ *t4#al 5 h? y y tt, 4WO^Tt/77Htt5.6«T*oft ~ 修 であった との «#»&. 重 合 挙 動 は,モール -t-^^t-t^-tstk* 埠 を 含 有 する 水 溶 Fig.2.7 fh**g#*po*fi&:7-n ^ t J tfig.2.8(c*-t-j: 5K/?71. $20#iSRS *ci!i»ih## ibna. *» «#/J ( dfttt, mftlftx. *>Kiry y hs-g-osnasft* * 7*-* #» #;?. > ft &**) 4l9~50tlOM»PKIBHT1.4~1.6O-S«[Tft-9^ ~ 彰,グラフト 効 率 2. O~

35 JABBI-M 9481 >*WkM-fhZ.tK&\> PET-* h 'J *, fxtii%bti>< J>, #< ^77 hkjs *^ bn&x.9k&&#{&t-tz>frtbtom%)%&».4>i.lt, be>t%a.bflz>o 60 MAA-(CH,Cl) 8 (3/2) 20% aq. [Cu*]-5x10" 2 mol /I 3.6xl0 4 rad/h Irradiation time, h Fig. 2,7 Grafting of methacrylic acid onto polyester fibers at 3.6X10 4 rad/h at different temperatures in the presence of ethylene dichloride. Monomer mixture, MAA:(CH2C1)2: Water=12: 8:80. by vol., concn. of copper sulfate 5X10" 2 jnol/1. E MAA-(CH t Cl) 1 20%aq. : [Cu*>5xKr*mo /I f0 40'C 19*C. J.4±a2 "0.1 Q Irradiation time, h Fig. 2.8 Log-log plot of the grafting curves shown in Fig. 2,

36 JAERI-M 9481 MMl, MLfeMAAO^l^?,?77 h$*«ijicl. /5 7 b«j^ &5 L7fc 0 9llffc*S * Table 2. ~ 5 Km^to 示 す 3.6XIo"rad/hの 6 X 10*r ad/li j»:t^t 線 量 率 で 2 時 B$Rg 間 の 照 JS&tTf± 射 では 4 0 *CT*fciH^^5 fj. ;?7f $ fc 2 0 C "Ctt 2 1 #«*" f 4 l^#. 4 0 C T 9 9 S, 50t, 6 5 C Ttt ioo*tc»l7fc. toig^^ibn^'fk^^v'^^^jplt ^"7 7 hs-g-4ff*5»'&ec% 4 o (e) «ft*(d^* MMMS. 1 9 t fcihot, m*m* 6.5X10 3 rad/n {> 1.6 X 10 5 rad/h- T^T^&L fcib#4fig.2.9 fc, til* log-log 7"o., - Lftfc Fig. ~ 2.10(^7^^- 示 す o Fig.2.10rc Fig.2L10fC*> 沿 ^TB««#tt*** C«*-r0 = L4 ffi*t*ofc, tiljt J>^7 7 h* 5*«:* «S" J2K ; i&, Fig.2.6 fce^ltzrltto C ^S2Ji 0.55T*o7t 0 Z^S-ffc* * i'j'* gsjbl-c^75:^7 5t K&tf&mtMms-'&ZTF-i- att0.51 -c*>z>frb. tltitf5.($n&<dm &.&&&-(:& 2>t^Z.2>o MA A&Wi»*^:S-a-l r <:i>^t«a = 0.65 t\n5fc&m j g- ti-c\r> Table 2.5 Graft-and homo-polymerization of methacrylic acid in the presence of copper sulfate (2) Monomer mixture, MAA: (CH 2 C1) 2 : Water»12 : 8 : 80, containing copper sulfate, 5 x 10~ 2 nol/ ; Irradiation, 10~ 3.6 x 10* rad/h., 2 h. Irradiation Apparent graft Total Graft temperature conversion efficiency C %» %

37 JAERI-M ou MAA-(CHjCl) 8 (3/2)20% aq. «40 _ lcu*]«5x10" e mol/l 4f 1.6xl0! rad/h 3.6x10 4 rad/h S xl0«rad/h 20 - CO a. < 10 s 6.5x10 3 rad/h i i i., Irradiation time. h» i i.. i i 10 Fig. 2.9 Grafting of methacrylic acid onto polyester fibers at 19 C at different dose rates in the presence of ethylene dichloride. Monomer mixture, MAA:(CH 2 C1) 2 : Water=12:8:80, by vol., concn. of copper 5X10-~ sulfate 5X10" 2 mol/1. O.5~.-O~ Irradiation time, Fig Log-log plot of the grafting curves shown in Fig

38 JAERI-M 9481 MA A7km%L% bvk i&ltx-? is ' Z^-t Z> MA A*ffSffl^5SiM* (Tig.2.3 ^.to^.s) id^77 h$5^ici->11->5,^77 Ml^lgtSfe. )よりグラフト 率 5~ち κ なけるグラフト 重 合 速 度 を 求 め, ifig.2.11 ^i»f,na. TU =t>^7-o -y h -fh -^ftx^i^v&^snl^^a-a-m^ffi^tt^-g-tt, miss oti^fj 8 6t «gh-c 7 ot!zmt-t2> * mm-v$kt>-gn, z.nx. jf^wofsfrfb* ** -«: 5 oc~7o tlt kcal/mol, 7 0 C ~ 8 6 "CTT 10.5 kca l/mo I t V* 5 fit## htl 2>o 70 CfeTFTf2 rj&ik*i-i'-s±tt-tz>*; *-WL*m\nitm, MMS 2 ot~5 o C»5H-c,.# frbfoftmt* * ""?-it 8.7 kcal/mol T*o7fc <Dmit~^it = * * * &S t H.^^% "C»W/7 7 t-m<&e>frfr!r}<dl&mk***" -X. S> $#ffi^ffit & & * - A'^4^JpL.feAA7k«iRS:ffl^^*'&H:Ml#T7KLfe < t 5K1 8 t~4 0tT&0 kcal /not, 50-9 OtJT 1.4 kcal/mol t 1^ 5t#f f)ftt IAI..? %.%>*>,&UWS&<D MM K& ^xa, ~m^t^^^yimmi±^'tk%, MA A ^? 7 h a-a-h, AA -enx 5 &?s loor «50h on a* "» 10 i DO a Temperature, *C ; OMAA-(CH 8 Cl) i B(3:2)20%aq. MAA 20 % aq Kcal/mol 226 Kcal/mol * 3.5 1/T xlo 8 Fig. 2,11.ns plot of the grafting rates of methacrylic a< d onto polyester fibers. ( ) 20% aqueous solution of MAA (0) MAA:(CH 2 CI) 2 : Water=12:8: jf * P U ^WLOify 7 Y m&vafrtrth Z-frtfommt* **>*- -32-

39 JAEEI-M ??y Ymmommmm Fig Microphotographs of cross-sections of methacrylic acid graft polyester fiber, (a) G=6.8% (b) G=12.6% (c) G=33.9%

40 3.5 iryy MRflftOftaft JABEI-M 9481 MA A? 7 7 H M& U : - ; tei7- h V 7 *i&$>2>v>l($.1}*'-yt> A^COI^T 2 5 "C, ~ 6 彰 6% pig.2.i3 rc»kiig*?*:* #, tohtcttikiiieo^toicaa^-77 vmm<d.m&$>7fi? 7 2 «:.is&{14><, 3 0*/77.$Ot<D?6!Rfi$tt4«T*4. CilttT ~ 彰 で 木 綿 念 みの 吸 湿 fi^sfjm, AA7-hV9At&f7 7t-mmKit'<iikfriic4$z,mg.<DM..&'ci>t). MA A Q ~ 20 gain ( o MAA-H A MAA-Na ^, a MAA-Ca AA-Na>-r^ x^* ^^\ / >^r MM-Na 3 10 S* ^S' Cotton 2. -jap^-«. SIO! < S'/ J ^ W c r. ^ ^ ^ t ^ * 5 * 1 ^ ^ Apparent graft, % Fig Moisture regain of methacrylic acid grafted polyester fiber at 66% R.H., 25 C. For comparison moisture regains of cotton, acrylic acid (AA)-graft, AACa-graft and AANa-graft polyester fibers are shown. 4. & fe PET,m^ &m&w%m%sk.2>maa<d?-?7hm-&k-z>\^xmmlfto PETmm ZM&m±mt L?ftBfflft«AlLfeMAAK*ffttK:8gtL. l9t3-l50to«k»c*'irti: i/^'i"^^^,, *«i^bp mw-e*.>eia.**# y^- i H:5 ocw± j -3 4-

41 JAERI-M 9481 mwl&l*-$tsmaa<drt.mmk, Btilfflk Lt =.&<k**i'rz:mmi-2>zk tie *>, MU t ^ 5 7 f n&&fi% 5Lk tiwlkfto MA A--JI{fcx * v y -fc<dm&l&.wl)!cft 1 2 ". 8 :8 0, K?^*5 x io*mol/0mtol&*s *-%l*fb\f*jtl&&. Wc%^y 7 bsekt m-&mm.ia.4 oc-c*{i,. 溶 液 相 {rc stfcffirc^a^tfy^- ^^.^^^**,, ;J;~けるホモポリマーの 生 成 もほとんど 抑 制 された Vx± 7 5 C KlE-CJi X 10 3 rad / h~ 3.6 X 10* rad / h jbft^olgffl T, 3 fc~s fki^u^&^trmaatk^^stffl^^l 9 C RIE-CK, 6.5 x 10 3 rad/ h~ 1.6X1 0 s rad 3-V y%<gt?ma A7kBW.%M^Z> R&- & 2 0 C ~5 0 "C JSgiSfflT a 7 kcal/mo 1 T& O7to 2fcfef$*t $fb SiS&tt!IK:.t >. M A A#'J ^-#«*!*«:# :*- *@ftt. mm4kft -&# jiff L X IA -6 : 25:fr^ ^ ^ 0 MAA^77 h* Na^ttT^ U ^$^7 7 h ft Na i H^PJgKKCiS^KSS^T^L &tz.?7 7 b %.fc >&frlrf > mmikx-** -k, M A A7kmfo*R1^2>RS&<fC*i L X tt 5 0 C~7 0 C taktght22.6 kcal/mol, 70~86 CT 10.5 kcal/mol T > J>, ~i it*- -35-

42 JAERI-M 'J A&frX CM 9 9»J ^Kfc /?7 ]>fi 1. *-yx^v>"ru7!?^-b (PET ). ^*?i9>&#v ^^ T- *fll.ffli<b2> V>tfft%4>M. * ~»& (mmft3-z&z.& **n&zwu-t & ) sr^flnlttt^ D*»(AA) **?. -art *ft(iaa^7 7hilOttS, JfcfctffeMA A^7 7 Htj ft«4aij5 L. IfCAA & l^fimaa ^5 7 H^Ki I), PET«j ris^tf»rc«7kfb3ft/fc^4jfc«tfcttl/fci g 2. nrntsfc 2.1 ^7 7 h *-y i^7-^isr g lsj r ^ ij ^ gj ^ 7 7 b * y x ^ T- ^ A A ^-7 7 hpettttrci 5rcpi»L7to im p ET t> litems n it ft-efi&^xm. it, 7fcT137:, it 72*50#^ ^ Ti#W;.0.012g/'cm 2 T^>o7to H^PET** Hillit, ftwk, %LW& 17cmX 22cm ^ 5i^-a]»fL. * t 21 cm X 21 cm (ft ft, Ifg 1 cm) <D^y-^ \s*my v AK1SL. 24 cm ( 5 ) x 22cm (ig) X 6 cm ( *ff ) * 7" J' レス v*»kj5^3s{caft, 製 反 応 容 器 κ 入 れ,モール *-**S*aP^.7fc60* 塩 を 加 えた 60~ 拶 AATKSfRC 水 溶 液 (モール *-^^«K 塩 濃 度 1 lxlcr2mol/~) X ict 2 mol/^) KgjJfLT, SiSt^TK 60 Co Ci#»e) r i»*22 ±1 tjofiktjutflfco is81:^w:1.6~2.4x10 4 rad/ht* i>, HSI-WK& Mfli> (C D, *MO/7?h$ 40«4TO8*O^?7 h^ ^" yy h*&&^7fc 40~ 彰 までの 種 々のグラフト 率 のグラフト 布 を 得 た AA/77f7^;^ htt^ ^KiB^jfegftftftfto Til!*! Life > ^ ^ y ^Si /?7 h*5i^f* 前 S8JtSi HlDPET*2:ffi^, 項 と 同 じ 布 を 用 い, 漫 m»mrbm%vt. 潰 法 r 線 照 射 K よ btaaafyy!>maa グラフト hftfchsglltfco 布 を 調 製 した す~わち, -*4*>t>. PETtt^fx v*«#cc@5gl. t-i* Jfi-ffc * * u-vfc 2 0 C-C2 OB&HSiH. ~mt^ fi'v*w^83*, #^7 7 h * y *- feeg*«3ftij-i--5 7ta&K6f a»^*g5jpl7fei 5* MAAfcmfo (ffi&mmm) l X lo^mol/^cgitl, ~ ii*1.0x ltfrad/horgi* 5 5 CTfi?,liLt ^77 hs-^stfitkc^o ^^lt ^7 7 t-$ J8Uhfu$IW M#&Fig.3.i MA A^7 7 b 7 -, 7 ^ >- h tttgzhefcjs^ttsaiftlbi^rswfc^otwsiltfc. -36-

43 JAERI-M 9481 I 2 a b I 10 a. < Irradiation time (h) Fig. 3.1 Grafting of methacrylic acid onto polyester fabrics at a dose rate of 1 x 10 rad/h at 5S C グラフトされたアクリル?yy\- Sti-fc-T 2 誠 ij :j;...~びメタクリル ^fel^'^ *? 'J *'8e ffi'v. <E& 酸 の 塩 への 転 換 rcgi»l. 8 0C-C2fflfeIt5eiiKJ:l), ^nfftnas, CaStflfe 0 /7 7h$H 2.2 ttft K T*' > - ^ - ppk5 BWiS^xRS^-yr. m*jijp*aij!el tk«i^*^:! L7to 2. 3 &*$ /S**'JtZ> : «'* ^? 7 h^ ^7 7 r ** $ * , 6 5*BHO*fl=K5 Bfel.±^o Tttl, *fc(fii:2 an<d&w:frb * = f * r ^- 7J<«( m~) Ca.0.3m^) を *&T3-, 落 下 させ,それが -tft#3fti 布 JC^^(CRJK^iXt*jRtC#5fr S*f**5ffi^-4-C0^FlH! ( wicking time) *SiJ L;fe -t7 ;b1p. wicking t ime *>"/>$ ^g, JfiJOR^gjRris^; n 2. 4 #»,W«S m^-fbif* = -* ).-.*#* * ^7-^^- 2 < ) 4ffl^rt 0 E2 5"C, *g*fil 4 5 2SRH (C*»^"CS IJ5 L/fc. K? A 0fijgH:7OOlHl/#-tr4>i>, ^7 7 rfttc500g ffi2fciwt, SPBT* C«L-E»IS*. WJMItti»ttO : V**Ett*ffl Lfe. -37-

44 JAEEI-M &,& ii?-* >$km t Ltd, Sevron BrilIiant Red Biffl^A. M M t S i l l l i ~ぢ. 2^, Na 2 S %, CH 3 COOH %-^^L. ~ 彰 含 有 し, I&it^50 浴 比 が : 1 (C7j S J: 5 felhsslitfc ^ifc&^tltfcteastman B Polyester Red B4ffllofe を 用 いた G &-fe tt*$*tmf: 染 色 浴 は 繊 維 重 量 の 2~ 2^ &«多 の 染 料 &fi$fl 4 > 1 g Disper TLit*, SfifcT 100 : 1 KH.&. JKHJBL^ jfcfeis' ±.va&&m,mi! i*mjtho Kic-to±*»?>2ootK*f,^i;j6jDsifcL^*«T>f * y*m.t, 25gf/cm ESTTi5#riftiLfei. f$$i)tte^**^ffil,m.mft &%i&t&mtt «fcslftfi:«2. 7 ihfef* (Limiting Oxygen Index) fcfflljigl. Iti & fpff L 7t 3.1 T ^ I I ^ S W O 1 ^ ^ ' ] *! ^ ^ h#iji^f *f(d issfc J; QfR 7k 14 «i.i>'77h(0aa/77h*o20t, 6 5«RHKi?ftaKS. ^zksecfi* Table 3.1 fc ^ L ±o AA/57 t> # #(C, ^77 ^ AA^# NaJ^&.5^ttCa^rc^ftL7tStW<:c>(/> t &g ifcl/t 0 # *& Table 3.1 (CT*3 ftt ^ 0 AA ± Y L.ft *T«ffifcStt RzkSO^SPfiffi/d'-C^a^. AA/?7h **AA-Na ^7 7 bfli ("Cgg^ Z. t K X t>. * CftftRIS, RzMStfs^ibftfco AA-Na?? 7 Yma.^7 7 b ^*SJI ~ち, 5%, 約 *t)5*-r-?r 59 援 でそ ^ fft^is&^okih*. R7jcf /$ 5 #ibtt&o AA-Na ^7 7 h ft(iaa^?7 htifflsi #S7fctoKtt/fl»!S;'!7ia^^7 7 H «H T I I S. -38-

45 JAERI-M Table 3«1 Moisture regain and wicking of water droplet of acrylic acid, sodium acrylate and calcium acrylate graft polyester fabrics at 20 C, 65* R.H. Apparent graft Moisture regain Wicking time % % sec Control AA AA-Na AA-Ca Cotton Gia. -39-

46 JAERI-M MAA/57 hftotltti?7 7 t- mom^ifig. 3.2 *lk*t AA^57 h ft KS^ttfeglfC^LTto Fig. a2 fe* 0*Jt;'<a <!:, MAA^77 h$chft(iaa/.77 \--% > % tit &[ $&.- $>2>Z.t ft t>fr2> MAA-Na/?7 r ffio&ffi&fi 10^.%V*f7 7 b $ dcthmaa/5 7 I- * f5 firing T2> ;ds, J- ^tfj 10^4 AA-or AA-Na-graft fabrics MAA-orMAA-Na graft fabrics Cotton 3 ^ / /* /*-AA-Na A/<MAA-Na Cotton <2.o.!~~ / - ^ -X>o-o "* A A I «"T I I I - t /WBT T. 1, Apparent graft (%) Apparent graft (%) Fig. 3.2 Moisture regain of polyester fabrics grafted with acrylic acid, methacrylic acid or their sodium salt at 25"C, 66% R.H.. Acrylic acid grafts (o), sodium acrylate grafts ( ), methacrylic acid grafts (a) and sodium methacrylate grafts {*). Dotted line shows the moisture cotton~ regain of cotton; ft*jsk KKife**Fig.3.3(C^-to I2(2AA / 7 7hf, ^ElfiMAA \- fik &-i-h% -c*><o. ^n^n?? 7 hmvta.mkmmi.jtf-7 7 ^ sbme^t^fctklfc. AA. MAA/? 7 f fit %W.<D : ]& %<Dl( r7 7 f mk85-it-f. wicking time tijzmft KfltCOUt 300fbfelJ:tr«)D. %.7Mt<DB&!l{C*ll-Z<lt^fifr~C$>-oft 0 AA-Na it 7 7 P fitt.w.%<d7 7 7 h$"cwi eking timed 10#feLT J), &? ^m^b^^l 7fc =? 7 7 ' t-m&&% : MZ.Xm*l- %Wt.-fc l &ll3.m-klftfr ift a MAA-Na /5 7 b ^ RTkfirH MAA/7 7 h ^rcjt^st^iltl^a^, AA-Na 757 r ftccji;-<s \&h frk' j),7 7 7 \-^tm±l-c trtmsttfa-fclfctf'ofc,? &*>*>, AA, MAA, MAA-Na ^7 7 Kffi R*&tt^JS*il&*L;d»fife ft*#» =. -40-

47 JABBI-M Fig. 3.3 Wicking time (time required for a droplet of water to be absorbed to fabric when it is placed on a surface of fabrics) vs. apparent graft at 23 C, 65% R.H. for polyester fabrics grafted with acrylic acid, methacrylic acid and their sodium salt. Symbols are the same as in Fig. 3.2 J.2 T^ y *m&iif t * i> y J^WLr?y i- * y x *?*'M<D1 W&%'&. PETmm<Dm^t<DEm<D oa, m»9m^±-t&ctx'i>h 0 mmttnvi±&*w **EfciBIJ5 L7fc. A A / 7 7 H, AA-Na ^? 7 h^(j(d*«sm^»ife**fig.3.40fe 0K, MAA ^? 7 h^5, MAA-Na?y 7 Y ^O^ttl *Fig *HfC^L 7fco AA/7?.f flj WS*BEH^5 7 h^^jf^-f Z>k J ttikfccx^-$>i&t-f2>&, 20% SStT ^77 b$t*$ * #* # e. fct:giit&-=7fc 0 AA-Na ^77 h ft-? MAA/? 7 rffi, MAA-Na^7 7 h ft»* RKilg * KI nfcc, MAA^7 7 h fttfct ^? 7 r sgolt^kiet-cwwabett^-f'ffit-ta^, **» #**flerc- -ch:{ TL;&2e>o7fc <> tftliaa/77 h*ih* ^ RlT*S 0 MAA-Na ^7 7 hfostftfimaa/? 7 b ft J fisf $ntwi 0 L 7> U 4 j$i t, **( 4* l l/vsf*fi:4?&srstt. ^?7H2 0*fel±«5i2.»T*> j). AA-N» ^7 7 l-ftktt; -:& imaa-na ^7 7 h ^ ^*Kit«)*tt^o-t: ^5 ftt>fr-o-tt a >300< O >3 30()i- A JtoA4*A ItJA JOfe/MAM^fe IJ 晶 ~& A A 300 A.<> A ~ o 100 > w 50 oaa c AA-Na I 10- A MAA 5 - c MAA-Na ' Apparent graft (%) Apparent graft (%) -41- ~ 彰 以 上 が 必 要 であ.þ

48 JAERI-M ,000 5,000' AA-or AA-Na graft fabrics ~ ~ 1,000 ~I j p tt?n _ 500 fo AA [ AA-Na!:i Apparent graft (%) A MAA-or MAA-Na graft fabrics A *A A * Cotton A [A MAA t A MAA-Na Apparent graft (%) Vi-g. 3.4 Electrostatic charge of polyester fabrics grafted with acrylic acid, methacrylic acid and their sodium salt at 23 C, 45% R.H.. Symbols are the same as in Fig i> y»wls3-zu* *? y»&.??? r *-y X^^-HUMI?!!-^ T ^ y ^^^ 7 7 h ^ ifefett AA^?7l-4 **ty^sevronbrilli8nt Bed B ftffl nas-fefufeig** Table 3.2(Cjp-t 0 Pk&USt 98"C T 90 frk&lrf 2>t %i-c*> h t SfCjSH/Vt D,tt**i 1 gsj) *i Sl RlR*: Cmg )*^^ ^^3=fT@ *e, ff«tt^«^ < t)^fecdi-a-%5s WTlMlifllJgLJfctOTr, l#ht<"ft. VttfgSfeaKtCL**ftL"t^*^iOT*4. igpet*fct*3 L *>'*fi(cs3l-c^<*-i b ^#, ^77 ~ h$10 ^&± ^7 彰 以 上 の 各 グラアト 7h$ 布 -ffc?fefleastniau Polyester Red B /f!<^ 3fcfii$l*ifg* Tab le 3.3 fcjj^0 ^?7 f-a^l 0 %&±<D %<D~CAA, AA-Na. Ai-C»/77Hp, fail 4 g p ETf. \> % < kk±<d 9(C, AAf? 7 r*p «*SfeflrcStf-tS*ft tta$jt*aris.»*e^k* 5 -f» -4 2-

49 JAERI-M 9481 Table 3.2 Dye affinity of acrylic acid graft polyester fibers to cationic dye (Sevron Brilliant Red B) and fastness of dyed fibers. Dyeing temperature, 98*C Apparent Df Color, Daylight ironing, rating % mg/g eye test fastness rating 1 ) Fastness to F~~~~~~S ~~~. 2) graft naked rating 2 ' Stain Discoloration Control JUL 0.7 C.9 IV 3 -> IV II I AA-Na,,a o IV IV II I ) I : excellent, II : good, III : fair, IV : poor, very poor. 2) The larger the number, the better the fastness. Table 3.3 Dye affinity of acrylic acid graft polyester fibers to disperse dye (Eastman Polyester Red B) and fastness of dyed fibers. Dyeing temperature, 120 C 1), 2) See table 3-2 Apparent Df Color, Daylight i~~~i~g; ironing, rating ;~ting2)' % mg/g eye test fastness Fastness to _. graft naked rating*' rating2) Stain Discoloration Control 11.1 Ill AA III III II I AA-Na III Ill II I AA-Ca III II II

50 . JAERI-M t * }> y -a-bs^? 7 b7^7^ybi->j: 2>'^ 3fefe^ MAA^77^^7^yf KCV^t, 1i?-* ^^^ Sevron Bri II iant Bed B ffll^ t. Btr^Ki>^St W ^ ^frt^feiclfe4fif75:o7to AA/77hO«^tM!)MAA7 7 7 h* $:fe tt«sit& ifc a L.frLO.ftb 7? 7.$10 ~ *MiOMAA-Na^77 彰 以 上 の MAA-Na グクヌトh ^HAIifTX^feeiTKLfeo MAA/77 bft. MAA-Na I- *& &-, (2? ^ 7^ x #ifc3fc;p Eastman Polyester Red B fcft-?-;&$:,* *& t L- ±o MAA/77f * $= fetttt^7 7h$20^t TSfit^/^oTt/SS. MAA-Na /J7f ^ tiuffi 5 & «:tt 7t^-feS^^fjtl7t 0 M A A^7 7 b PET$OSfittBAA/7 7 h PET KJt^S i:7>7s{)#so ^tlfel_h3j; M±i ^7t, 5JCAA^77h PETiMAA^77 b P E T HTM &&?& b. \&W. m&ftm&tti A A h fercib-^. MAA/77 h%«^7j: tj^otti^sl^^^tlts^-r, MAA/?7 h *$> * & t> ilit A A? y 7 hftkjt-it^tid^ot ^ # 5 fc>7>o ±o MAA^57 HittHSHAA^77 >%o<d4:tlbffl&&.-t:>h kfclfrfrtob-i'. &7jc z.nb<dtfc?k<dmmc'&3l-oti&t>ixz>. z.nbomgom.mc^^-i's-'&'dfflftk-iittzits n.bh.^0 r? 7 h«t*i a*e«)e«(c-oir.tmaaj: J> AA^7 7 YmM.o-jsft&.nit'm&.-km-tz. 3.4 T^!lA.i^77b*, iji^f*oii^ T^iJ*8/?7htO«ttffiia8 AA^7 7 h ^ Tfet %fa<d&-j3, #K. 5IS5SK ibijj ils** Table 3.4fC7J^- 0 K«O^Hrea5cm, ;1<5 6 cath, 151 D & *tt$l 3S5IS 1 0 cm/bin "CifJJtL 7to 5IS^*fct. ttoitlxfakl cm gi A*l. I3S3K1 0cn»/iDiaTiSIJSL7to Table 3.4 K&btl&X. OUC ft OffitJ ti A A 7? 7 ] S.-k IfC. ^>X Iti, fibasb&ftl X\^it^0 /? 7H#!)iifitS(C5fttf Of 5#J At* T, ^ffi^s*7ti> ^ A A7? 7 hfl, Na«Ke«LftKflTtt. I3I?SA, SlS&fefc K«ffiT L A. WAA/?7h ^ S&ElftttHIC&trt-ftJlBIJOigffftai-^Tfc. *-*y7-^7.-k y-^-sffl^. loo^^m^tm, &* # * suss L&, mmm<d$ft)twm<dmb&k. Klfe *& Table 3>5»CJj*-*. -44-