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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(
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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
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