Page 1 34 2 Vol. 34 No. 2 Journal of Materials Science & Engineering

0 downloads 0 Views 514KB Size Report
Jun 2, 2015 - Based on UV-curable Epoxy Acrylate Resin. REN Peng-fei ... The organic oligomer ... by the combination of UV-curable urethane-acrylate. 2.
材 料 科 学 与 工 程 学 报 Journa l o f  Ma t e r i a l s  Sc i enc e  & Eng i ne e r i ng  

第34卷   第2期 Vo l. 34 No. 2

总第160期 Apr. 2016

文章编号: 2016) 02-0181-07 1673-2812(

epa r a t i on  and  Pr ope r t i e s o f  Ha r d  S c r a t ch-r e s i s t an t  Coa t i ng s Pr   Ba s e d  on  UV-c u r ab l e  Epoxy  Ac r l a t e  Re s i n y Peng-f e i,WANG  L i,YU  Hao-j e,TIAN  Zh i-f e i,REN  Fu-j e,DENG  Zh eng, REN  i i h eng,Za i n-u l  Abd i n,Muhammad  Sa l e em CHEN  Yong-s ( o f  Ch emi c a l  Eng i n e e r i ng,Co l l e e o f  Ch emi c a l and  B i o l o i c a l  Eng i n e e r i ng, Labo r a t o r t a t e  Ke S     g g y  y  , , ) Un i v e r s i t zhou  310027 Ch i na Zh e i ang  y Hang j

【 Ab s t r a c t】 UV-cur ab l e epoxy  a c r l a t e r e s i n( EA)wa s syn t he s i z ed  by t he r e a c t i on  o f epoxy r e s i n           y     wi t h  a c r l i c a c i d.The r e su l t i ng  EA  wa s copo l r i z ed  wi t h  3-me t ha c r l oxy  opy l t r ime t hoxys i l ane         y yme y pr (MPS)a s a coup l i ng  agen t unde r  UV  i r r ad i a t i on t o  ob t a i n t he s c r a t ch-r e s i s t an t coa t i ng.The  epa r ed               pr UV-cur ab l e,ha rd  and t r anspa r en t coa t i ngs  we r e t e s t ed  by  va r i ous  me t hods such  a s  ha rdne s s t e s t,t ape           adhe s i on t e s t and  s c r a t ch  r e s i s t anc e t e s t.Re su l t s ob t a i ned f r om  t he s e i nve s t i t i ons showed t ha t t he                   ga ope r t i e s o f t he coa t i ngs  we r e impr oved  wi t h t he i nc r e a s e i n t he con t en t o f s i l ane coup l i ng  agen t.                         pr The rma l behav i o r f he t i ngs wa s l so s t ud i ed and t wa s ound ha t he he rma l t ab i l i t f    o  t  coa  a  i  f  t  t  t  s y o coa t i ngs  wa s impr oved  by t he i nco r r a t i on  o f s i l oxane.       po   】 【 ; wo r d s  UV-cur Ke ab l e coa t i ngs epoxy  a c r l a t e r e s i n;s c r a t ch-r e s i s t anc e     y y  CLC  numbe r: TQ323. 5  Do cumen t c ode: A  DOI: 10. 14136/ cnk i. i s s n  1673-2812. 2016. 02. 002   j.

UV 固化的环氧丙烯酸树脂耐磨加硬涂层的制备及性能 任鹏飞 ,王   立 ,俞豪杰 ,田志飞 ,任福杰 ,邓   正 ,陈永盛 , i n-u l  Abd i n,Muhammad  Sa l e em Za (浙江大学化学工程与生物工程学院,化学工程国家重点实验室,浙江 杭州  310027)

EA),然后用硅烷偶联    【摘   要】  本文通过环氧树脂和丙烯酸为原料反应合成了环氧丙烯酸树脂( 剂 3- 甲基丙烯酰氧丙基三甲 氧 基 硅 烷 (MPS)对 其 进 行 改 性,得 到 可 紫 外 光 固 化 的 有 机 硅 耐 磨 透 明 涂 层,并对涂层的各种性能进行了测试,如硬度测试、附着力测试和耐磨性能测试等。结果表明,相比未涂 覆的有机玻璃基材,涂覆后的有机玻璃基材的表面硬度和透光率均有所增加 ,且随硅烷偶联剂含量的增 加而有所提高。对耐磨涂层的热稳定性也进行了研究,结果发现,改性后的环氧丙烯酸树脂的热稳定性 要明显好于未改性的。 【关键词】 UV 固化涂料;环氧丙烯酸树脂;耐磨性能

1 I n t r odu c t i on

t r anspa r enc r, poo r c r a t ch r e s i s t anc e  s y. Howeve l imi t s t he app l i c a t i on  o f  PMMA  i n  many  me chan i c a l l     y []

Tr anspa r en t l a s t i c s  po l t hy l   p   such  a yme ( ) me t ha c r l a t e PMMA ha s be en wi de l ed n  i y y us , va r i ous app l i c a t i ons  due t o i t s l ow  cos tl i t  we i t,         gh gh

emedy o r h i s agg r e s s i ve i t i ons1 . The  r  t  cond  f

impa c t r e s i s t anc e,t he rma l s t ab i l i t and  op t i c a l     y  good 

A  va r i e t o f soph i s t i c a t ed  oc e s s i ng t e chn i s   y  pr que  

ob l em  i s t he  us e  o f t r anspa r en t ha rd  coa t i ng f i lm  a s       pr   apr o t e c t i ve l aye r f o r  PMMA  subs t r a t e sur f a c e.      

c e i v e d  da t e: 2015-04-30;Mod i f i e d  da t e: 2015-06-02 Re B i o r aphy:REN  Peng-f e i( 1989- ),Ma l e,Ma s t e r,Re s e a r ch f i e l d:s c r a t ch-r e s i s t an t c oa t i ng. E-ma i l: 1989guoyunyu@163. c om.     g Co r r e s i ng  au t ho r:WANG  L i( 1957- ),E-ma i l:op l_ wl@d i a l. z u. edu. cn. j pond

材料科学与工程学报

· 182 ·

2016 年 4 月

have be en us ed o r he pr epa r a t i on o f he c r a t ch  f  t  t  s

i nve s t i t i ons showed ha t he pr ope r t i e s f i d    t  t  o  hybr ga

r e s i s t an t r anspa r en t o t e c t i ve t i ng o r PMMA  t  pr  coa  f

coa t i ngs oved  wi t h he nc r e a s e n he   impr  t  i  i  t

subs t r a t e. The t i ona l e chn i s nvo l ve  conven  t  i que

mod i f i c a t i on r a t i o. The t ruc t ur e o f i spheno l A  s  b

[ 2-4]

and ed chemi c a l r depos i t i on l a sma-enhanc  vapo p [ 5-7] aqueous t i ng pr oc e s s e s .Nowadays,t o me e t  coa

epoxy e s i n r t s many exc e l l en t ope r t i e s n  impa  pr  i  r coa t i ng app l i c a t i ons. Howeve r,i t s he a t e s i s t anc e  r

ab l e t i ngs r e h i t anda rds ndus t r  coa  a  i gh s y, UV-cur

and  i c a l ope r t i e s a r e  no t enough.The  us e       phys pr good 

be i ng  deve l oped i n  an  e f f o r t t o r educ e any  de t r imen t a l         e f f e c t o he i r onmen t,and a r e ge t t i ng much  t  t  env

o f s i l ane coup l i ng  agen t t o  mod i f b i spheno l  A  epoxy       y 

i n t e r e s t o owe r r t i on, l e s s  due  t  l  ene gy consump , env i r onmen t a l l l u t i on h i chemi c a l s t ab i l i t and     po gh  y  [ 8,9]

r e s i n  c an impr ove i t s  i c a l r f o rmanc e i n  coa t i ng         phys pe e s i s t an t app l i c a t i on. The l i c a t i on o f c r a t ch-r  app  s coa t i ng  con t a i n i ng bo t h b i spheno l A epoxy a c r l a t e y



r e s i n and s i l ane l i ng agen t n dome s t i c  coup  i  and

UV-cur o t e c t i ve ab l e coa t i ngs r e wi de l ed o r    a  f  pr y us

ve r r ap i d cur i ng even a t i en t empe r a t ur e  amb  t y  

e and t h i s  k i nd  o f f o rmu l a t i ons cons i s t o f one             purpos

f o r e i r e s e a r ch  r epo r t s  wa s  no t  much. gn  , I n t h i s  r b i spheno l  A  epoxy  a c r l a t e r e s i n     pape y

t os ens i t i ve C=C bonds,wh i ch c an be o r  mo r e pho

and s i l ane l i ng  agen t MPS we r e l i ed  coup  app

l r i z ed  by  UV  i r r ad i a t i on.The  o rgan i c o l i r   po yme gome

s imu l t aneous l n s c r a t ch-r e s i s t an t t i ng by he  coa y  i  t

r oups i ng f unc t i ona l c an  be f unc t i ona l i z ed  wi t h      g pend  

r e a c t i on  o f t he  UV-cur ab l e epoxy  a c r l a t e r e s i n  wi t h       y

[ 10]

t o o rm a e cond ne two rk .I n he i e l d o f UV  f  s  t  f cur i ng ndus t r i e s, b i spheno l Aepoxy and epoxy  i

MPS.By i nve s t i t i ng t he e f f e c t o f  MPS  con t en t on       ga     ope r t i e s f he t i ng, we ound he t he pr  o  t  coa  f  t

a c r l a t e  de r i va t i ve s  have  be en  wi de l us ed i n  coa t i ng,   y y 

ope r t i e s o f r e l a t i onsh i be twe en t he s t ruc t ur e and          pr p 

s t ruc t ur a l s i ve s ed  compos i t e   adhe   and  advanc

coa t i ngs. The ob t a i ned coa t i ngs we r e e s t ed by  t ha rdne s s e s t, t ape s i on e s t c r a t ch-  t  adhe  t  and s

[ 11-14]

.B i spheno l  A  epoxy r e s i n  d i f f e r s f r om     l r s  due t o i t s exc e l l en t chemi c a l,so l ven t o t he r           po yme , ope r t i e s and r e s i s t anc e good t he rma l and  adhe s i on        pr ma t r i c e s

r e s i s t anc e t e s t.The t he rma l behav i o r o f t he coa t i ngs             wa s a l so s t ud i ed.    

[ 15]

epa r ed pr

ve r s a t i l i t n c r os s-l i nk i ng.S.W.Kim y  i

ope r t hybr i d  coa t i ng  ma t e r i a l s  wi t h  an t i-abr a s i ve  pr y

r imen t a l 2 Expe

by t he comb i na t i on  o f  UV-cur ab l e  ur e t hane-a c r l a t e   y  

2. 1 Ma t e r i a l s

r e s i n  sys t em  and  s i l i c a t e  ne two rk  v i a so l oc e s s. l -ge     pr i no rgan i c hybr i d coa t i ngs ba s ed on cyc l oa l i t i c pha

oduc t s f TCI Epoxy r e s i n( EA03)wa s he pr  o  t   ( , Tokyo Chemi c a l ndus t r i Ch i na ).  I y Shangha ( TPP ) Tr i l i ne and  3- pheny phosph

epa r ed by so l epoxy a c r l a t e pr l e chn i -ge  t y que.L.

me t ha c r l oxypr opy l t r ime t hoxys i l ane (MPS ) we r e y

e a S. Ka r a t a s t  l

[ 16]

r epo r t ed UV-cur ab l e o r i c- gan

[ 17]

epa r ed UV-cur ab l e r ans r en t  t pr pa ur e t hane-a c r l a t e (UA)r e s i n hybr i d ma t e r i a l i ng  us y Zhang e t l  a

[ 12]

cha s ed f r om  Fl uka.Ac r l i c a c i d  and  EtOH  we r e     pur y cha s ed r om  Shangha i c a l  Re agen t   f   Chemi pur

us ed

Co rpo r a t i on.I r cur e 184 wa s  cha s ed f r om  C i ba     ga pur

s i l i cone o mod i f e s i n o ob t a i n s c r a t ch  t  t y epoxy  r r e s i s t an t t i ng  and nve s t i t ed he t i ng   coa  i  t   coa ga

Spe c i a l t c a l s. Al l e agen t s we r e us ed a s  r y Chemi r e c e i ved.PMMA subs t r a t e s( 6cm ×6cm ×0. 5cm)

ope r t i e s o f t he mod i f i ed epoxy e s i n.The r e su l t s       pr  r

we r e  us ed i n  a l l coa t i ng  app l i c a t i ons.    

i nd i c a t ed ha t t i ng  ob t a i ned  had  exc e l l en t  t   coa [ 18] , adhe s i on ha rdne s s oughne s s.F. Hanwen  and  t

2. 2 Pr e r a t i on  o f b i s l  Aepoxy  a c r l a t e r e s i n     pa pheno y ) ( ( EA03 10g and r i l i ne 0. 02g)  t pheny phosph

syn t he s i z ed s i l oxane mod i f i ed epoxy a c r l a t e e s i n  r y

we r e r ans f e r r ed n t o 50mL t hr e e-ne cked ound-  t  i  r , bo t t om f l a sk equ i t h n i t r ogen n l e t  i  and pped wi

TMSPM a s l i ng agen t.Y.L i t l  a  coup  e  a

i s t ur e dua l l ed coa t i ngs wh i ch and UV-mo y  cur , exh i b i t ed impr oved  ha rdne s s we a r i ng  r e s i s t anc e and     [ 19]

wa t e r t a c t l e. G. Bay r amog l u   con   ang

us ed

d r opp i ng f unne l.The r e a c t i on  mi x t ur e  wa s  he a t ed t o      

s i l ane coup l i ng agen t o mod i f i spheno l  IPTMS  t y b

70℃ and s t i r r ed o r n unde r n i t r ogen.Ac r l i c  f  30mi y a c i d ( 4. 03mL,6. 05mL and 8. 07mL)wh i ch wa s

Aepoxy a c r l a t e e s i n o ob t a i n UV-cur ab l e ha rd  r  t y

co r r e sponded t o  Samp l e 1-3wa s added t o t he r e a c t i on            

t r anspa r en t i d coa t i ngs. Re su l t s r om t he  hybr  f

mi x t ur e  d r op  wi s e r e spe c t i ve l and t hen t he  mi x t ur e       y 

第 34 卷第 2 期

任鹏飞,等 .UV 固化的环氧丙烯酸树脂耐磨加硬涂层的制备及性能

wa s he a t ed a t o r t t a i ned  80℃ f  abou  4h. The ob oduc t wa s l e a r i s cous i i d. To pur i f he  c  v  l pr qu y  t oduc t,we  wa shed  o f f exc e s s a c r l i c a c i d  by  wa t e r 5         pr y

· 183 ·

ana l e r f r om  20t o  700℃ wi t h  he a t r a t e  o f 1TGA      yz 10℃/mi n.The  UV-v i s spe c t r a  o f t he s amp l e s  we r e      

t ime s,f o l l owed  by  a c e t one and  cyc l ohexaneone t ime,    

i s spe c t r opho t ome t e r (Hi t a ch i  UV- r e co rded  on  UV-v   3000)a t  wave l eng t h  o f 200-700nm.Hyd r ophob i c i t   y

t he ob t a i ned pr oduc t wa s pu t n t ova cuum oven a t  i

wa s r a c t e r i z ed by wa t e r t hy l ene g l l  cha  and e yco

30℃ f o r n o rde r o u l l r t i c i t e n he  8h.I  t  f  i  t y pa pa r e a c t i on  o f epoxy r e s i n,d i f f e r en t  mo l a r r a t i o  o f epoxy        

con t a c t l e on OCA 20supp l i ed by Da t aphys i c s.  ang Penc i l ha rdne s s  wa s t e s t ed  a c co rd i ng t o  GB/T  6739-      

r e r e s i n and a c r l i c a c i d wa s l e  added.Samp  1-3 we y ( ( ) ) , n EA03 ∶n a c r l i c a c i d =1∶2 1∶3 ob t a i ned  wi t h    y

1996.The t ape adhe s i on  wa s  de t e rmi ned  a c co rd i ng t o      

and  1∶4,r e spe c t i ve l y.

coa t ed  PMMA subs t r a t e  wa s done by r s i ng n  imme  i , , / wa t e r 10 wt. % NaOH 0. 1mo l L HCl  and

2. 3 Pr epa r a t i on  o f s c r a t ch-r e s i s t an t c oa t i ng     ( A mi x t ur e o f s r a c t i on)epoxy  90-91 % ma  f i l ane coup l i ng  agen t  MPS  and a c r l a t e r e s i n,1-2% s     y , 2% pho t o i n i t i a t o r r a c u r e 8 4 l e v e l i n a e t,  Ig  1 g  g n de f oame r s, d i spe r s an t s e a c t i ve d i l uen t s wa s  and  r

ASTMD  3359-95.The chemi c a l r e s i s t anc e t e s t o f        

/L NaCl 0. 1mo l oob s e r ve t i ng  appe a r anc e  t  coa / / GB T  9265-2009. a c co rd i ng t o  GB T  1733-1993and    Sc r a t ch r e s i s t anc e e s t wa s l ua t e dus i ng he  t  eva  t f o l l owi ng  appa r a t us a s shown i n  F i 1.       g.

s t i r r ed  a t 25℃ f o r 0. 5h.Samp l e 4-6co r r e s t o         ponded 1. 0 % ,1. 5 % and 2. 0 % s i l ane l i ng agen t  coup epa r ed homogeneous MPS, r e spe c t i ve l y. The pr l sus i ng  Box- f o rmu l a t i on  wa s coa t ed  on  PMMA    pane t t i ng dev i c e (QTG, PUSHEN ). Be f o r e  coa ype l s we r e l e aned us i ng e t hano l coa t i ng,PMMA pane  c /L  /L  and1. 67mo l NaOH/0. 189mo l Na2CO3 so l u t i ons ( i f t r a t e f a c e.Coa t i ng equa l vo l ume)t o pur  sur   ysubs f i lms  we r e  ob t a i ned  by  i ng l i t s ens i t i ve  v i s cous   pour gh   , l s cur i ng wi t h a h i l i i d on he PMMA pane  t gh qu e s sur e( 1000W)UV-l amp ( SP-100P,Spe c t r on i c s) pr f o r 60si r r ad i a t i on f r om  30cm  away.     2. 4 Cha r a c t e r i z a t i on

i 1 Schema t i c t e s t d i ag r am  o f s c r a t ch  r e s i s t anc e  o f c oa t i ngs F         g.

3 Re s u l t s and  d i s c u s s i on   3. a c r l a t e r e s i n 1 Pr e r a t i on  o f b i s l  Aepoxy      y pa pheno The b i spheno l Aepoxy  a c r l a t e e s i n wa s  r y epa r ed  by t he r e a c t i on  o f b i spheno l  A  epoxy r e s i n     pr    

The  FT-IR spe c t r a o f he c r l a t e e s i n  t  epoxy a  r y

wi t h a c r l i c c i d a s n Scheme  a  shown  i  1. The y

we r e e co rded be f o r e f t e r i f f e r en t UV-cur i ng  r  and a  d by  a  Ni co l e t c t r ome t e r (Ni co l e t   5700 spe

s t ruc t ur e o f i spheno l Aepoxy a c r l a t e e s i n wa s  b  r y

I ns t rumen t s, Mad i son, WI). The amp l e s we r e  s

-1 The pe ak a t s s s i o he  a  t  t  2889cm   wa gned

epa r ed  by l i i d  membr ane  me t hod.The s t ruc t ur e   pr qu  

b i s l  A  epoxy  a c r l a t e s t r e t ch i ng  o f  C-H.The  pheno y

o f t he c r l a t e e s i n wh i ch wa s pr epa r ed by    epoxy a  r y

r e s i n  showed  s t r ong  s i l s a t 1725cm-1 f o r t he  C=C       gna

1  H- a c r l i c a c i d  and  epoxy r e s i n  wa s cha r a c t e r i z ed  by      y  

s t r e t ch i ng bend i ng wh i l e he c t rum o f he pur e  t  spe  t

NMR on AVANCE Ⅲ 400.The rma l r av ime t r i c  g r  Py r i s ana l i s  TGA  wa s c a r r i ed  ou t on  Pe rk i n-Elme     ys     

cha r a c t e r i z ed  by  FT-IR  a s shown i n  F i 2.     g.

b i spheno l A epoxy e s i n showed no i l s n h i s  s  i  t gna  r -1 r eg i on. The r t i on band a t s  adso  3463cm   wa p

     

Scheme 1 Syn t he s i s  o f b i spheno l  Aepoxy  a c r l a t e r e s i n       y

材料科学与工程学报

· 184 ·

2016 年 4 月

F i 2 FT-IR  s c t r a  o f e  b i spheno l  Aepoxy r e s i n   g. pe pur   ( a-EA)andb i spheno l  A  epoxy  a c r l a t e r e s i n   y ( b-s amp l e 1,c-s amp l e 2,d-s amp l e 3)      

a s s i o he O-H s t r e t ch i ng o f he i ng  t  t  t  epoxy gned  r i nd i c a t i ng suc c e s s f u l i ng-open i ng. The s e  epoxy  r r e su l t s showed t ha t b i spheno l  Aepoxy  a c r l a t e r e s i n         y

i 3 1H-NMR  s c t r a  o f b i spheno l  Aepoxy  a c r l a t e r e s i n F     g. pe y ( A-s amp l e 1,B-s amp l e 2,C-s amp l e 3)      

[ ]

wa s suc c e s s f u l l syn t he s i z ed19 .   y  The t he s i s f i spheno l A epoxy a c r l a t e  syn  o  b y 1 

e s i n  and  MPS  by  UV  i r r ad i a t i on  a s shown i n  Scheme r    

r e s i n  wa s con f i rmed  by H-NMR  a s shown i n  F i 3.       g.

2.F i 4 showed FT-IR spe e b i spheno l c t r a o f  pur g.

Typ i c a l s i l s appe a r ed  a tδ=3. 90-4. 45ppm  we r e     gna , a s s i o H-e H-f n he b i spheno l A  and H-g  t  t gned  i

Aepoxy  a c r l a t e r e s i n  and  b i spheno l  A  epoxy  a c r l a t e   y y , r e s i n  mod i f i ed wi t h MPS.As shown n  F i 4 t he    i g.

epoxy  a c r l a t e r e s i n.A  s t r ong  s i l a tδ=1. 72ppm     y gna

mod i f i ed b i spheno l Aepoxy a c r l a t e e s i n showed  r y

wa s a s s i o -CH3 o f i spheno l A.The i c a l    t  b  t gned yp , s i l s a tδ=6. 27 δ=6. 05andδ=5. 59ppm  we r e   gna

s t r ong  s i l s a t 3447cm-1 wh i ch  wa s a s s i t o t he         gna gned S i-OH s t r e t ch i ng. Me anwh i l e,i t i s t i nc t  showed d

and  e s enc e  o f  C H-ddue t o t he  a s s i t o  H-i,H-j       pr gned   =C i n t he a c r l i c a c i d.B i spheno l  A  epoxy  a c r l a t e         y y

-1 -1 ak a t cha r a c t e r i s t i c  ng  1235cm  and 1181cm  owi pe [ 20] and S r oups , i-O-S i t o t he appe a r anc e o f i-O-C         S g

r e s i n  wa s suc c e s s f u l l syn t he s i z ed  by t he r e a c t i on  o f     y   

i nd i c a t i ng ha t MPS wa s mod i f i ed wi t h b i spheno l  t

b i spheno l  A  epoxy r e s i n  wi t h  d i f f e r en t  mo l a r r a t i os o f       i e l d o f 67% , a c r l i c c i d, wi t h a e a c t i on y  42.  a  r y

Aepoxy  a c r l a t e r e s i n  suc c e s s f u l l   y y. 3. 3 Pr ope r t i e s o f s c r a t ch-r e s i s t an t c oa t i ng      

66. 67% and  88. 67% ,r e spe c t i ve l t hough  a c r l i c y.Al y a c i d  wa s no t u l l r t ed n t o he pr oduc t,t he  f  i  t y conve

ope r t i e s 3. 3. 1  The rma l ope r t i e s    The rma l  pr  pr

h i r mo l a r a t i o o f c r l i c c i d a c i l i t a t ed he  r  a  a  f  t ghe y r a t i on  o f b i spheno l  A  epoxy  a c r l a t e r e s i n.     gene y

DTG  ana l i s s n F i 5.Al l he amp l e s  a  shown  i  t  s ys g. , showed  abou t 20% we i t l os s a r ound  100℃ wh i ch       gh

3. 2 Pr epa r a t i on  o f s c r a t ch-r e s i s t an t c oa t i ng    

cou l d  be t he  de compos i t i on  o f l ow  mo l e cu l a r  we i t     gh

o f t he coa t i ng  ma t e r i a l s  wa s  de t e rmi ned  by  TG  and    

t o po l r i z a t i on o f i spheno l Aepoxy a c r l a t e  b pho yme y

l r.When he we i t os s wa s e a ched up o  t  l  r po yme gh  t , 50% a l l t he s amp l e s showed  d i f f e r en t de compos i t i on        

   

    

The c r a t ch-r e s i s t an t t i ng wa s pr epa r ed by  s  coa

Scheme 2 Syn t he s i s  o f s c r a t ch-r e s i s t an t c oa t i ng  ma t e r i a l      

第 34 卷第 2 期

任鹏飞,等 .UV 固化的环氧丙烯酸树脂耐磨加硬涂层的制备及性能

· 185 ·

ope r t i e s, e spe c i a l l t s rbanc e n he UV  abso  i  t y pr  i r ange.The e f f e c t o f  MPS  con t en t on  coa t i ng’ s l i t         gh t r ansmi t t anc e  wa s shown i n  F i 6.I n t he r ange  o f         g. wave l eng t h( v i s i b l e l i t),compa r ed o 400-700nm   t gh 92%l i t t r ansmi t t anc e  o f b l ank  PMMA  subs t r a t e,     gh l i t t r ansmi t t anc e o f t ed PMMA subs t r a t e wa s    coa gh i nc r e a s ed  up t o  93% ,due t o t he f a c t t ha t t he s c r a t ch-               r e s i s t an t t i ng had a owe r e f r a c t i ve ndex han  coa  l  r  i  t PMMA  subs t r a t e. F i 4 FT-IR  s c t r a  o f b i spheno l  Aepoxy  a c r l a t e r e s i n     g. pe y ( a-s amp l e 3)and  b i spheno l  A  epoxy  a c r l a t e r e s i n     y

epa r ed 3. 3. 3   Phys i c a l ope r t i e s     The pr  pr

amp l e 6) mod i f i ed  by  MPS ( b-s  

coa t i ngs we r e r a c t e r i z ed by he l i s o r  cha  ana  f ys  t , ope r t i e s s ha rdne s s adhe s i on, va r i ous pr  such a

t empe r a t ur e Td.The Td o f he b i spheno l Aepoxy  t

t r ansmi t t anc e i r onmen t e s i s t anc e. The  and env  r

f t he s amp l e 4- r e s i n  appe a r ed  a t 385℃ wh i l e t he  Tdo           6wa s a t 390℃ ,418℃ and  426℃ ,r e spe c t i ve l l     y.Al

r e su l t s  we r e shown i n  Tab l e 1.The coa t ed  PMMA        

t he amp l e s o r de compos i t i on a r ound  s  showed ma j 350℃ wh i ch mi t o he t i on o f  be due  t  t  combus gh

t r ansmi t t anc e a s shown i n  F i 7.Compa r ed t o  b l ank         g. PMMA  subs t r a t e,coa t ed PMMA subs t r a t e had an

r oups i n t he b i spheno l A epoxy o rgan i c f unc t i ona l        g

i nc r e a s ed  ha rdne s s f r om  HB  t o  6H.Th i s i nc r e a s e i n      

a c r l a t e r e s i n  ba ckbone.The i nc r e a s ed  Td i nd i c a t ed     y an nc r e a s e n he rma l t ab i l i t f he t i ng  i  i  t  s  t  coa y o

t t he  ha rdne s s  wa s a t t r i bu t ed t o  a l koxys i l ane      pendan t-cur r oup’ s  hyd r o l i s and  i ng  v i a condens a t i on.     pos g ys

ma t e r i a l s  wh i ch  wa s a t t r i bu t ed t o t he i n t r oduc t i on  o f        

The adhe s i on t e s t i nd i c a t ed t he coa t i ng  had  exc e l l en t          

s i l ane coup l i ng  agen t  MPS.   ope r t i e s    Op 3. 3. 2  Op t i c a l ope r t i e s f i c a l t    o  pr pr

ope r t t ed PMMA subs t r a t e adhe s i on pr y. When coa wa s r s ed n d i f f e r en t c a l s o r  imme  i  chemi  f  7 days,

t he coa t i ng  ma t e r i a l s a r e c r i t i c a l i n  some f i e l ds such             a s  op t i c a l f i be r coa t i ngs,l ens coa t i ngs,and  so f o r t h.        

ope r t i e s f t ed PMMA chemi c a l e s i s t anc e pr  o  coa  r , subs t r a t e  wa s e l l en t pr ov i d i ng  a e l i ab l e   exc  r

The we a t he r e s i s t i v i t l so depends t i c a l  r  on op y a

r an t e e f o r t he i r env i r onmen t a l r e s i s t anc e.         gua

subs t r a t e l e a r i lm appe a r anc e wi t h h i  showed c  f gh

   

F i 5 TG ( a)and  DTG ( b)cur ve s  o f b i spheno l  A  epoxy  a c r l a t e r e s i n  and  b i spheno l  A  epoxy  a c r l a t e r e s i n  mod i f i ed  by  MPS ( Samp l e 4-6)         g. y y

Tab l e 1 Phy s i c a l r op e r t i e s o f unc o a t e d  and  c o a t e d  PMMA  s ub s t r a t e s         p Samp l e  Unc oa t ed 

F i lm  appe a r anc e  Penc i l ha r dne s s   

Adhe s i on 

Wa t e r r e s i s t anc e  Ac i d r e s i s t anc e  Al ka l i r e s i s t anc e  Sa l t r e s i s t anc e        

Opaque 

HB



l e 4 Samp  

C l e a r  

5H

4B

Unchanged 

Unchanged 

Unchanged 

Unchanged

Samp l e 5  

C l e a r  

6H

4B

Unchanged 

Unchanged 

Unchanged 

Unchanged

Samp l e 6  

C l e a r  

6H

4B

Unchanged 

Unchanged 

Unchanged 

Unchanged









t h  coa t ed  and  uncoa t ed  PMMA  sur f a c e s  we r e   Bo

d i d  no t d i sp l ay  any  s c r a t ched l i ne s,whe r e a suncoa t ed      

con t i nuous l rubbed unde r oad o f t h an  a  l  100g wi y ( ) abr a s i ve  r 600# i n  o rde r t o  a s s e s s t he s c r a t ch       pape

PMMA  sur f a c e eve r e l f f e r ed r om  t h i s  s  f y  su s c rubb i ng. Bo t h  coa t ed  and  uncoa t ed  PMMA

r e s i s t anc e pr ope r t e e t ed PMMA sur f a c e s  coa y.Thr

subs t r a t e s we r e t i nuous l t t ed o h i s  con  t  t y submi

材料科学与工程学报

· 186 ·

F i 6 L i t t r ansmi t t anc e  o f unc oa t ed  and  c oa t ed     g. gh

2016 年 4 月

F i 8 Sc r a t ch  r e s i s t anc e  o f c oa t ed  PMMA  subs t   g.

PMMA  subs t r a t e s( Samp l e 4-6)  

r a t e s( a-s amp l e 4,b-s amp l e 5,c-s amp l e 6)      

l e 2 Mi n imum  we i t l o ad  mak e s c r a t ch e s app e a r Tab         gh MPS/wt.%

An t i-s c r a t ch/g

B l ank



20

Samp l e 4   

1. 0 

25

Samp l e 5   

1. 5 

30

l Samp e 6   

2. 0 

35

Samp l e 

ang l e s o f he t i ngs aus ed by va r i a t i ons n MPS    t  coa  c  i F i 7 Pho t og r aphs  o f unc oa t ed ( a)and  c oa t ed ( b)   g. PMMA  subs t r a t e  by  s amp l e 6  

rubb i ng  and t hen  we i we i t l os s o f eve r         ghed.The  gh y 20 rubb i ng cyc l e s wa s nd i c a t o r o r c r a t ch  an  i  f  s r e s i s t anc e. I twa s e r ved ha t t ed PMMA  obs  t  coa subs t r a t e  by  s amp l e 6showed l e s s  we i t l os s r e l a t i ve       gh t o  s amp l e 4and  s amp l e 5a s shown i n  F i 8.We a l so           g. wi he t i ng sur f a c e wi t h a we i t oad  t  coa  l ped gh s andpape r o epr e s en t c r a t ch r e s i s t anc e o f t ed  t  r  s  coa , PMMA subs t r a t e t he mi n imum we i t oad made  l gh

con t en t  we r e shown i n  F i 9.Compa r ed t ouncoa t ed       g. PMMA  subs t r a t e,con t a c t ang l e s o f bo t h  wa t e r and         l l i nc r e a s ed  wi t h nc r e a s i ng  MPS e t hy l ene  g  i yco , conc en t r a t i on r e a ch i ng t o  max imum  va l ue  o f 101. 1     and 83. 3, r e spe c t i ve l i s e r va t i on wa s  obs y. Th r owi ng MPS a t t r i bu t ed o he a c t ha t wi t h g  t  t  f  t , con t en t t he nc r e a s i ng numbe r f -OS i (CH3 )  i  o 3 r oups i n he ne two rks e ad o he nc r e a s e nwa t e r  t  l  t  t  i  i g l l con t a c t ang l e f r om  87. 2t o  101. 1and  e t hy l ene      g yco con t a c t ang l e f r om  64. 1t o  83. 3.    

4 Conc l u s i on

s c r a t che s appe a r  wa s l i s t ed i n  Tab l e 2.        

A s e r i e s f UV-cur ab l e t i ngs wi t h h i  o  coa gh

Hyd r ophob i c i t s r a c t e r i z ed by wa t e r  cha y wa , con t a c t ang l e and i nc r e a s i ng  va l ue  o f  wa t e r con t a c t      

t r ansmi t t anc e and  s c r a t ch-r e s i s t anc e  ope r t i e s  we r e   pr

ang l e r e f l e c t ed i nc r e a s e i n  hyd r ophob i c i t r i a t i ons       y.Va

epa r ed.The t he rma l s t ab i l i t o f t he  ne two rks  wa s       pr y 

i n t he va l ue s f wa t e r t hy l ene g l l t a c t    o  and e  con yco

s i i f i c an t l impr oved  by t he  mod i f i c a t i on  o f  MPS  t o gn y    

   

   

i 9 Schema t i c  d i ag r am  o f t he c on t a c t ang l e s:( r  b l ank  PMMAsubs t r a t e,( r s amp l e 4,( r c oa t ed  s amp l e 5, a)H2O  b)H2O  c)H2O  F ove ove ove               g. ( d)H2O  ove r s amp l e 6,( t hy l ene  l o l ove r  b l ank  PMMAsubs t r a t e,( t hy l ene  l o l ove r s amp l e 4,( t hy l ene e)e f)e             g yc g yc g)e t hy l ene  l o l ove r c oa t ed  s amp l e 6 h)e l o l ove r s amp l e 5,(             g yc g yc

第 34 卷第 2 期

任鹏飞,等 .UV 固化的环氧丙烯酸树脂耐磨加硬涂层的制备及性能

epoxy  a c r l a t e e s i n r e l a t i ve o pur e c r l a t e  r  t  epoxy a y y r e s i n.Th i s i nc r e a s e i n t he rma l s t ab i l i t wa s r e l a t ed           y  i nked dens i t f he t em. The t o he r os s-l  t  sys  t  c y o hyd r ophob i c i t i r onmen t a l e s i s t anc e o f he  r  t y and env

· 187 ·

Bu l l e t i n,2002,47( 5):437~444. [9 ] Kayaman-Apohan  N,Demi r c i  R,Cak i r  M,e t l.UV-cur ab l e  a /v i n t e r t r a t i ng  l r  ne two rks  ba s ed  on  a c r l a t e i ny l e t he r pene po yme y f unc t i ona l i z ed  ur e t hane o l i r s[ J].Rad i a t i on Phys i c s  and gome Chemi s t r 5):254~262. y,2005,73(

coa t i ngs l so oved.I t wa s ound ha t he  a  impr  f  t  t

[ 10] Ch i ang  C, Ma C M,e t l.The rmo-ox i da t i ve de r ada t i on o f  a g

add i t i on o f MPS n epoxy a c r l a t e e s i n cou l d  i  r y

nove l epoxy  c on t a i n i ng  s i l i c on  and  spho r ous  nano c ompo s i t e s   pho

impr ove t r an s a r e n c o f c o a t i ng.Ha r dn e s s and  s c r a t c h       p y  r e s i s t an c e  r op e r t i e s o f t he c o a t e d  PMMA  s ub s t r a t e  we r e       p f ound t o  b e  r e a t l imp r ov e  d r e l a t i v e t o  un c o a t e d  PMMA     g y   s ub s t r a t e. The s e o a t i ng s wi t h h i r an smi t t an c e,  c  t gh e s i s t an c e nv i r onme n t a l e s i s t an c e an b e s c r a t c h-r  and e  r  c a r t s. u s e d  wi d e l i n  many  op t i c a l   p y   Re f e r enc e

[ J].Eur ope an  Po l r J our na l,2003,39( 4):825~830.   yme [ 11] Kim  J  W,Suh  K D.Amph i i l i c  ur e t hane a c r l a t e hyd r oge l s   ph y hav i ng he t e r opha s i c ge l t r uc t ur e: swe l l i ng behav i o r s  s  and me chan i c a l r ope r t i e s[ J].Co l l o i d  and  Po l r  Sc i enc e,1998,   p yme 276( 4):342~348. [ 12] L i  Y. T,Zhang  N.,Ca i  H.,e t a l.Syn t he s i s and  r ope r t i e s  o f     p s i l i c one  mod i f i ed  epoxy r e s i n[ J].J our na l o f  Ma t e r i a l s  Sc i enc e  &     Eng i ne e r i ng,2009,( 01):58~61. [ 13] Wang  H.,Wang  Y.,L i L.,Han  D.S t udy  on t he  Syn t he s i s     and p r ope r t i e s o f c r l a t e e s i n mon tmo r i l l on i t e nano-  epoxy a  r y

[1 ] Yava s  H,Se l  Uk  C  D  Z,Zhan  A  E  S,e t a l.A  r ame t r i c s t udy     pa l s i l i c a c oa t i ngs  on on  r o c e s s i ng  o f s c r a t ch  r e s i s t an t hybr i d  s o l-ge         p l a r bona t e[ J].Th i n  So l i d  F i lms,2014,556:112~119. po yc [2 ] Za íˇ ckováL,Bur  í ková V,J an  ca o t e c t i on c oa t i ngs o r ˇ  J.Pr  f j l a r bona t e s  ba s ed  on  PECVD  f r om  o r s i l i c on f e eds[ J].   po yc gano Va cuum,1998,50( 1):19~21. [3 ] Ta e s chne r K,Ba r t z s ch H,Fr a ch P,e t l.Sc r a t ch r e s i s t an t  a t r on-p op t i c a l oa t i ngs on po l r s by magne a sma-enhanc ed l  c yme chemi c a l vapo r s i t i on[ J].Th i n So l i d F i lms,2012,520    depo ( 12):4150~4154. [4 ] Dama s c eno J  C,Cama r J r  S  S,Cr emona  M.Depo s i t i on  and     go eva l ua t i on o f DLC-S i r o t e c t i ve oa t i ngs o r po l a r bona t e  p  c  f yc ma t e r i a l s[ J].Th i n  So l i d  F i lms,2002,420:195~1994. [5 ] Wi nk l e r R, Ar c E, e t l. Aqueous we t oa t i ngs o r  a  c  f pa J].Th i n  So l i d  F i lms,1999,351( 1): t r anspa r en t l a s t i c  l a z i ng[   p g 209~211. [6 ] Aege r t e r  M  A,Alme i da  R,Sou t a r  A,e t a l.Coa t i ngs  made  by   s o l-ge l and chemi c a l t e chno l ogy [ J].J our na l f l-Ge l  o  So    nano Sc i enc e and  Te chno l ogy,2008,47( 2):203~236.   [7 ] Schmi d t  H.New  t o f non-c r t a l l i ne s o l i ds  be twe en i no r i c       ype  ys gan and  o r i c ma t e r i a l s[ J].J our na l f Non-c r t a l l i ne So l i ds,  o gan ys 1985,73( 1):681~691.

c ompo s i t e ma t e r i a l s [J].J our na l f Ma t e r i a l s Sc i enc e &  o Eng i ne e r i ng,2004,( 06):906~908. [ 14] Ti an  Z.,Chen  H.Deve l opmen t o f  mod i f i ed  epoxy  a c r l a t e f o r     y UV-cur v i ng c oa t i ngs [ J].J our na l f Ma t e r i a l s Sc i enc e &  o Eng i ne e r i ng,2004,( 01):95~97. [ 15] Kim. S.W.Cha r a c t e r i z a t i on  o f uv  cur ab l e  hybr i d ha r d  c oa t i ng   ma t e r i a l s p r epa r ed by s o l-ge l me t hod[ J].Ko r e an J our na l f  o 1):298~303. Chemi c a l  Eng i ne e r i ng,2011,28( [ 16] Ka r a t a  S,Ki z i l kaya  C,e t a l.Pr epa r a t i on  and  cha r a c t e r i z a t i on  o f   s o l-ge l r i ved uv-cur ab l e o r i l i c a-t i t an i a hybr i d c oa t i ngs  de gano-s [ J].Pr og r e s s i n  Or i c  Coa t i ngs,2007,60( 2):140~147.   gan [ t l.Cha r a c t e r i z a t i on and 17] Zhang  L,Zeng Z H,Yang J W,e  a /s r ope r t i e s o f ab l e po l e t hane-a c r l a t e i l i c a hybr i d  uv-cur p yur y he o l-ge ma t e r i a l s p r epa r ed by l r o c e s s [J]. Po l r  s  p yme  t I n t e r na t i ona l,2004,53( 10):1431~1435 [ 18] Fe H.,L i W.,L i u  A.Syn t h e s i s  o f s i l ox a n e  mo d i f i e d ng   J.,Fu    a c r l a t e r e s i n  a nd  e r f o rma n c e  o f  UV-mo e i s t u r e  du a l l c u r e d   y p poxy  y  c o a t i ng s[ J].Pa i n t  & Co a t i ng s I ndu s t r 02):1~5.   y,2013,( [ 19] Bay r amo  l u G, Kahr aman M V, e t l. Syn t he s i s ˇ  a  and g cha r a c t e r i z a t i on  o f ab l e dua l i d o l i r s ba s ed on  hybr  uv-cur gome c r l a t e on t a i n i ng pendan t l koxys i l ane g r oups [J]. epoxy a  c  a y Pr og r e s s i n  Or i c  Coa t i ngs,2006,57( 1):50~55.   gan

·

[ 8] Ⅰnan  T  Y,Ek i nc i  E,Kuyu l u  A,e t a l.Pr epa r a t i on  o f nove l  UV-    

[ 20] Zhang.C.Pr epa r a t i on  and  cha r a c t e r i z a t i on  o f s c r a t ch-r e s i s t anc e  

cur ab l e me t ha c r l a t ed ur e t hane e s i ns r om a mod i f i ed epoxy  r  f y

t i c a l l a s t i c [D ]. Xi amen and an t i r e f l e c t i ve oa t i ng on op  p  c

r e s i n and s o c t oe t hy lme t ha c r l a t e ( IEM )[ l r J]. Po  i yana y yme

Un i ve r s i t y,2008.

檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿檿 o f  Cu( I n, Ga)( S) h i n f i lms  r epa r ed  by  c o-s t t e r i ng f r om Se,   pu p 2t   (上接第 203 页) [ 12] L i i ang  L i,Ye Yuan,Lan Hong,Hu i  Shen,Shan Ren.The q Cu2S  ho l l ow-c a c t us a r r ays:A  nano s t r uc t ur e  wi t h  a l a r r nano      ge spe c i f i c sur f a c e r e a ed i t o r t i on p r ope r t i e s    a  and enhanc  l  abs gh p [ J].Ma t e r i a l s  Le t t e r s,2013,300~303. [ 13] Yoon  H P,e t l.Enhanc ed c onve r s i on e f f i c i enc i e s o r p i l l a r  a  f

t e r na r a l l oy  and I n2S3 t a r t s[ J].Phys i c a  B,2011,406:   qua y  ge 824~830. [ 15] Tena-Za e r a R, e t l. Anne a l i ng Ef f e c t s on he Phys i c a l  a  t Pr ope r t i e s  o f El e c t r odepo s i t ed ZnO/CdSe Co r e-She l l Nanowi r e Ar r ays[ J].Chemi s t r o f  Ma t e r i a l s,2007,1: 1626~1632. y 

a r r ay  s o l a r e l l s abr i c a t ed r om c r t a l l i ne i l i c on wi t h sho r t  c  f  f  s ys

[ 16] L i e r r e B,e t l.Ef f e c t f i z e-Dependen t  C, Bando Y, Di  a  o  S

mi no r i t c a r r i e r d i f f us i on l eng t hs[ J].App l.Phys.Le t t,2010,     y 

The rma l ns t ab i l i t t he s i s o f Zn2S iO4-S iOx Co r e-she l l  I y on Syn

96: 213503—213503-3. [ 14] L i n  Y  C,e t a l.I n f l uenc e  o f anne a l i ng t empe r a t ur e  on  r ope r t i e s     p  

Nano t ube  Ar r ays and  The i r  Ca t hodo l umi ne s c enc e  Pr ope r t i e s[ J].   Nano s c a l e  Re s  Le t t,2010,5: 773~780.