교수정인우 - knubh.knu.ac.kr/~inwoo/paper/2011adhesion.pdf · 2011-05-12 · • urushiol/uv...

한국 접착 및 계면 학회 “2011년 정기총회 및 학술발표회”한국 접착 및 계면 학회 “2011년 정기총회 및 학술발표회”

교수 정인우

경북대학교 응용화학과inwoo@knu ac kr

2011-05-12 12011-05-12 1

[email protected]


> Research Background

UV 광중합 공정에 의한 제조된 강판 코팅은 최근 전자 및 가전 기기의 외관의 수려함과 고급화에 필수적인 소재이다 다른 중합 기법에 의해 광중합은의 수려함과 고급화에 필수적인 소재이다. 다른 중합 기법에 의해 광중합은비교적 높은 광택도를 나타낸다. 그러나 광택성에 미치는 여러 가지 공정 변수에 대한 영향에 대한 체계적인 상관 관계에 대한 연구가 부족하다. 또한 최근 높은 내식성이나 항균성이 요구되는 코팅 공정에서 사용되는 첨가또한 최근 높은 내식성이나 항균성이 요구되는 코팅 공정에서 사용되는 첨가제들은 광택성을 저하시키는 주요 원인이 된다.

Research Scope(1) Optimization of UV coating formulation for better gloss(2) Effects of urushiol for gloss, anticorrosive and antibacterial properties( ) g , p p

2011-05-12 22011-05-12 22011-05-12 2



Urushiol based lacquer

h l i f hi l d i i 60– The lacquer consists of urushiol derivatives (60-70%), water (~20%), other water or oil-soluble proteins, laccase, and gums (~10%).

– It has been well known that the urushiolderivates bring out allergy and they can be easily purified from the lacquer by solvent extraction with various nonpolar or polarextraction with various nonpolar or polar organic solvents.

– Physical propertiesPhysical properties• Boiling point : 210~220 °C• Appearance: Dark brown, viscous liquid• Derivatives: Catechols having unsaturated alkyl

chains

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chains



Urushiol 관련 연구 동향

on 25

30

PatentArticle

46.5%16.6%6.4%

of P

ublic

atio

15

20

Num

ber o

5

10 30.5%

Year1920 1940 1960 1980 20000

2007 Scifinder® Scholarship

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2011-05-12 52011-05-12 52011-05-12 5

IW Cheong et al., Prog. Org. Coat 65 (2009) 341.



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Free-radical polymerization of Pristine Urushiol p y

BeforeBefore UV irradiation

Under UV irradiation Thin film formation

on the surface

Urushiol Monomer

Under UV irradiation

Urushiol Monomer

Cross-sectional view

Volumecontraction

500

Volumecontraction

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Free-radical polymerization of Pristine Urushiol

O

p y

OH

hR

OH

OH

R

h

OHO Inhibition

R

OH

h&

retardation

OO

R

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R



UV Photo-polymerization of Pristine UrushiolUV Photo polymerization of Pristine Urushiol

Before

After

O-H

R

OHO

=C-HAfter C=O OHOH

R

hR

R

R

OHO

C-O

1000150020002500300035004000

R

• Decreases in OH & carbon double bonds

• Formation of carbonyl (C=O)

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Wave number (cm-1)

한국 접착 및 계면 학회 “2011년 정기총회 및 학술발표회”

> Results and Discussion: Chemical Modification of Urushiol

Modified of Urushiol with mono IsocyanateCH2

CH3OH

Chemical Modification of Urushiol

C

CH3

CH2

C

CH3

HNC

OOH 3-isopropenyl-α,α-dimethylbenzyl isocyanate

O

OH

R

benzyl

R

isocyanate

CNHO

H2C

O

CHNO

CHNO

Reaction conditionO

O CNH

H2C

O O

R

Reaction condition- Reaction temp.: 40 oC- Reaction time: ~2 hr- Catalyst: SnOct2- Solvent: THF

2011-05-12 112011-05-12 11

R

R Solvent: THF- Equimolar reaction



f f h l


Purification of Urushiol

1. Dissolve in methylene chloridey2. Stirring for 1 hr under N23. Decanting lower phase4. Filtration with a paper filter

%)

C=OO-H str.=C-H str.

mitt

ance

(%-CH2-

C-H

Aromatic

C=C str.

C-O str.Tr

ansm str.

=C-H

1000200030004000

C H bending

2011-05-12 122011-05-12 122011-05-12 12

Wavenumber(cm-1)



d l f f d


Proton NMR Spectra and GPC Elution of Purified Urushiol

UrushiolMn : 463Mw : 469PDI : 1.01

Monomeric units

400MHz@25oC, in CDCl3

Mn : 1260Mw : 1446PDI : 1.14

@40oC, in THF (1mL/min)

Oligomeric units

Retention Time (min)16 18 20 22 24

in THF (1mL/min)

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> Results and Discussion: Chemical Modification of UrushiolChemical Modification of Urushiol

Elemental Analysis of Purified Urushiol

OHR =Molar(%) Exp. Calc. Atom #

Carbon 37 0 38 2 21 OH

R

Carbon 37.0 38.2 21

Hydrogen 59.2 58.2 32**

Oxygen 3.8 3.6 2

Nitrogen 0* 0 0

Total 100 100 55*0 02 molar% of nitrogen was found

where, R=C15H31-2n, n = 0,1,2,3

0.02 molar% of nitrogen was found.**It varies depending on the number of carbon double bond.

2011-05-12 142011-05-12 14



FT-IR Analysis

-OH

FT IR Analysis

-NH

-NH

PUHI-MUBI-MUTMI MU (1 2)

N=C=O C=O

Wavenumber (cm-1)1000200030004000

TMI-MU (1:2)TMI-MU (1:1)

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Wavenumber (cm )



H-NMR Analysis

HI-MU 1H-NMR

H NMR Analysis

HN

H2C C

H2

H2C C

H2

H2C

O H2 H2 H2

CH3a

b ccc

de

O

C

O

CO NH

H2C C

H2

H2C C

H2

H2C CH3a c

cc d

b

e

* -CH -CH - -CH -

-CH3

-CH2-CH2-1.9

R**

*6.7

-CH2-CH2-2.5

-CH2-c1.3

-CH=CH-CH=CH-

-CH=CH-CH=

-1012345678910

b1.6 d 0.9a 3.2-3.3 e 6.6CDCl3

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ppm



H-NMR Analysis

BI-MU 1H-NMRH2 a

H NMR Analysis

O

O

C

ONH

2C

C

O

NH2C

a

a

bc

R

NH bc*

**

a 7.0-7.3 * 6.7

-1012345678910

b 4.2c 6.6

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ppm



H-NMR Analysis


H NMR Analysis

H-MU 1H-NMRH MU H NMR

C

OHN

CH3

C

CH3

CCH3

CH2

a

b

ed

c

O

OH

C CH3 bc

*

*

e 7.2-7.3

b 1.2R*

* 6.7

-1012345678910

c 1.5d 6.9 a 4.9,5.1

2011-05-12 182011-05-12 18

ppm



Microscopic Images of the UV-cured Films with HI- and BI-modified Urushiol (without UV Coating Solution, on Glass Substrate)Substrate)

HI-UR Film BI-UR Film

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> Experimental: Materials

Oligomers

Oligomers : (1) Minimizing volume contraction, (2) viscosity control, (3) crosslinking reaction, (4) functionality and compatibility.g y p y

Type Advantages Disadvantages

High flexibilityUrethane acrylate

(UA)

High flexibilityHigh elasticity

High gloss

High costHigh viscosity

E l tFast curing

Epoxy acrylate(EA)

Fast curingChemical resistance

CheapHigh viscosity

Polyester acrylateLow viscosity

Polyester acrylate(PEA)

yHigh flexibility

CheapChemical resistance

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Oligomers

General relationship between characteristics of oligomers and curing rate

Slow Curing Rate Fast

Small Molecular weight Large

and curing rate

Small Molecular weight Large

Low Viscosity High

Mono- Functionality Multi-

SmallFraction of monomer

Large

* 분자량 (통상 점도와 비례)이 클 수록 termination 속도 (통상 점도에 반비례)가 낮아져curing 속도가 증가한다. Free-radical 중합에서 중합 속도는 kp(f kd/kt)0.5의 속도 상수에비례함.

2011-05-12 212011-05-12 212011-05-12 21



MonomersMonomer : They act as a reactive diluent to adjust formulation viscosity and that will be incorporated into the polymer network.

General characteristics of UV monomer

Functionality Reactivity Viscosity Adhesion

General characteristics of UV monomer

mono- monomerdi-monomer

multi-monomer

slow

fast

low

high

good

poor

same No. of

low Mw

high Mw

slow

fast

low

high

good

poor

function-ality

Acryl monomer

Methacrylmonomer

fast

slow

low

high

poor

good

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> Results and Discussion: Types of Urushiol

110

HI-MU 농도에 따른 광택도110

Urushiol의 농도에 따른 광택도

Types of Urushiol

70

80

90

100

OS

S(G

U)

60708090

100

OS

S(G

U)

30

40

50

60

1 wt % 4 wt % 7 wt % 10 wt %

GLO

30405060

1 wt % 4 wt % 7 wt % 10 wt %

GLO

110

TMI-MU 농도에 따른 광택도

1 wt.% 4 wt.% 7 wt.% 10 wt.%

110

BI-MU 농도에 따른 광택도

1 wt.% 4 wt.% 7 wt.% 10 wt.%

70

80

90

100

110

SS

(GU

)

70

80

90

100

110

SS

(GU

)

30

40

50

60

1 t % 4 t % 7 t % 10 t %

GLO

S

30

40

50

60

1 t % 4 t % 7 t % 10 t %

GLO

S

2011-05-12 232011-05-12 23

1 wt.% 4 wt.% 7 wt.% 10 wt.% 1 wt.% 4 wt.% 7 wt.% 10 wt.%


> Experimental : Anticorrosive Analysis

h d lMethod: Salt Spray Test ISO 12944• Urushiol/UV coating samples were applied onto the electro-

galvanized steel plates (150mm×75mm donated by POSCO) withgalvanized steel plates (150mm×75mm,donated by POSCO) with a bar coater and dried in a convective oven at 80 ◦C for 12 h.

• The average thickness of coating layer was 5±0.5m. • The steel plates were wetted by spraying with a 5 wt.% aq. NaCl

solution for 24, 48, and 72 hrs at ambient conditions.

2011-05-12 242011-05-12 242011-05-12 24

한국 접착 및 계면 학회 “2011년 정기총회 및 학술발표회”한국 접착 및 계면 학회 “2011년 정기총회 및 학술발표회”> Results and Discussion:

Anticorrosive Analysis

SST (2 t 72h)

y

(2 coat- 72h)

0% 5% 10% 30%

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SST

y

(1 coat- 24h)

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0% 5%



SST

y

(1 coat- 24h)

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10% 30%



SST

y

(1 coat- 24h)

0%0%

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SST

y

(1 coat- 24h)10um

30%

10um

30%

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24 hrs

y

72 hrs

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> Experimental : Antibacterial Analysis

h d S 2801 3 1 C f 2 hMethod: JIS Z 2801 at 37±1 ◦C for 24 h• Cell types: Staphylococcus aureus (ATCC6538P, S. aureus) and Escherichia

coli (ATCC8739, E. coli). • Antimicrobial activity (R) was calculated according to Equation:

where A is the average number of viable cells of bacteria immediatelyafter inoculation on the control (untreated) sample, B, the average number of viable cells of bacteria on the control sample after 24 h, and C is the average number of viable cells of bacteria on the Urushiol/UV coating samples after 24 h.

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Antibacterial Analysisy

Antibacterial Analysis

PU-UV-PI 10%HI-UV-PI5%HI-UV-PIPU-UV-PI 10%HI-UV-PI5%HI-UV-PI[ (Test sample), After 24h / HI-MU ]

R=2.0(99.0%)[ (Test sample), After 24h / UV+5%UR ] R=2.7(99.8%)

[ (Test sample), After 24h / 10%UR ] R=1.0(90.1%)

10%BI-UV-PI 10%TMI-UV-PI

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[(Test sample), After 24h / TMI-MU ]R= 6.2(99.99%)

[(Test sample), After 24h / BI-MU ] R=0.9(88.1%)


Antibacterial Analysisy

6

7C

)

5

R =

(logB

/C

3

4

1

2

0UV 5 wt.%

PU10 wt.% PU

5 wt.%HI-MU

5 wt.%BI-MU

10 wt.%HI-MU

10 wt.%BI-MU

10 wt.%TMI-MU

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U U HI MU TMI MU


Acknowledgment: This work was supported by POSCO (광양제철소 표면처리연구소) from 2008 to 2010.

2011-05-12 342011-05-12 34

교수정인우 - knubh.knu.ac.kr/~inwoo/paper/2011adhesion.pdf · 2011-05-12 · • urushiol/uv...

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