Novel Light Stabilizers for Coatings...Copyrights reserved by Everlight Chemical Industrial Corp,...
Transcript of Novel Light Stabilizers for Coatings...Copyrights reserved by Everlight Chemical Industrial Corp,...
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Sep. 2019
Novel Light Stabilizers for Waterborne UV-Curable
Coatings
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Why Should We Use Light Stabilizers forWaterborne UV-Curable Coating?
Degradation
Coatings
Chalking
Color change
Cracking
Delamination
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Damage from UV light
UV-A400nm-320nm : 88%Polymer Degradation
Skin Suntan
UV-B320nm-280nm
9%Polymer
DegradationSkin Sunburn
UV-C<280nm
3%The ozone
layer blocking
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Polymer Stabilization
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O2
X X*hv R.RH
O2
O21
ROO.
ROOH RHRH
X is chromophore
RO.
UVA
HALS
Antioxidants
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Conventional UV-curing system
Photoinitiator Light Stabilizer
UV Light
Need UV light to generate
free radical for curing
Absorb UV light and terminate
free radical to prevent
degradation
Reduce line speed
Increase cost
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The criteria for UV package in UV-curable system
• Not competing with UV energy.
• High compatibility with UV-curable resins.
• No effect on initial color.
• No interference with production speed.
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The Novel Light Stabilizers for Waterborne UV-Curable Systems
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NLS = Novel Light Stabilizers
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16Min. energy to reach curing need (J/cm2)
3% NLS
2% NLS
1% NLS
Blank
NLS is not affecting curing speed for UV-curable coatings
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Dispersion test in Waterborne UV Curable Resin
(10g UVA/100g Waterborne Polyurethane UV Resin)
filter
Traditional UV Absorbers:Difficult to Disperse in Waterborne Systems
Fail
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Dispersion test in Waterborne UV Curable Resin
filter
The Novel Light Stabilizers for Waterborne UV-Curable Systems
PASS
(10g UVA/100g Waterborne Polyurethane UV Resin)
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Customers usually run into two problems when using UVAs
in the waterborne UV-curable coating
1. Difficult to Disperse in Waterborne Systems
2. Conflict of UVA and Initiator in UV-curable Systems
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New Light Stabilizers forWaterborne UV-Curable Coating
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Model Formulation
Materials Characteristic Structure
Waterborne UV-
Curable Resin
Polyurethane Dispersion
( for water-based system ) ---
Photo-initiator
50% α-Hydroxyketone
+ +
50% Benzophenone
Table 1 Compositions of waterborne UV model formulation
Ingredients Characteristic
AUVA
(for Water-based system)
NLS Formulation of novel light stabilizers
BHALS
(for Water-based system)
Table 2 Classification of light stabilizers
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Table 3 Details of screening design with different light stabilizers and test results
RUN Pattern A NLS B DFT
The min. energy to
reach curing need
(J/cm2)
1 ++-- 1% 1% 0 15 0.108
2 --+- 0 0 1% 15 0.123
3 -++- 0 1% 1% 15 0.123
4 +-+- 1% 0 1% 15 0.197
5 -+-- 0 1% 0 15 0.071
6 ---- 0 0 0 15 0.071
7 +++- 1% 1% 1% 15 0.197
8 +--+ 1% 0 0 15 0.108
9 ++-+ 1% 1% 0 50 0.057
10 --++ 0 0 1% 50 0.063
11 -+++ 0 1% 1% 50 0.063
12 +-++ 1% 0 1% 50 0.065
13 -+-+ 0 1% 0 50 0.051
14 ---+ 0 0 0 50 0.051
15 ++++ 1% 1% 1% 50 0.065
16 +--+ 1% 0 0 50 0.057
Screen Design of Light Stabilizers for Waterborne UV-Curable Coatings
Curing condition: 1x150w/cm2 (High pressure Hg lamp)
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Table 4 Parameter Estimates
Influence of Waterborne UV Absorber
Term Estimate Std Error t Ratio Prob>|t|
Intercept 0.1179286 0.006255 18.85 <.0001
A 0.02975 0.004584 6.49 0.0013
NLS 8.327e-17 0.004584 0.00 1.0000
(A-0.5)*(NLS-0.5) -8.67e-18 0.009168 -0.00 1.0000
B 0.04025 0.004584 8.78 0.0003
(A-0.5)*(B-0.5) 0.0165 0.009168 1.80 0.1318
(NLS-0.5)*(B-0.5) 1.735e-18 0.009168 0.00 1.0000
DFT -0.001879 0.000131 -14.34 <.0001
(A-0.5)*(DFT-32.5) -0.001471 0.000262 -5.62 0.0025
(NLS-0.5)*(DFT-32.5) -1.74e-17 0.000262 -0.00 1.0000
(B-0.5)*(DFT-32.5) -0.001729 0.000262 -6.60 0.0012
For W-UVA, the Influence of curing energy was about 10.1%
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For W-HALS, the Influence of curing energy was about 18.6%
Table 4 Parameter Estimates
Term Estimate Std Error t Ratio Prob>|t|
Intercept 0.1179286 0.006255 18.85 <.0001
A 0.02975 0.004584 6.49 0.0013
NLS 8.327e-17 0.004584 0.00 1.0000
(A-0.5)*(NLS-0.5) -8.67e-18 0.009168 -0.00 1.0000
B 0.04025 0.004584 8.78 0.0003
(A-0.5)*(B-0.5) 0.0165 0.009168 1.80 0.1318
(NLS-0.5)*(B-0.5) 1.735e-18 0.009168 0.00 1.0000
DFT -0.001879 0.000131 -14.34 <.0001
(A-0.5)*(DFT-32.5) -0.001471 0.000262 -5.62 0.0025
(NLS-0.5)*(DFT-32.5) -1.74e-17 0.000262 -0.00 1.0000
(B-0.5)*(DFT-32.5) -0.001729 0.000262 -6.60 0.0012
Influence of Waterborne HALS
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For NLS, the Influence of curing energy was about 0%
Table 4 Parameter Estimates
Term Estimate Std Error t Ratio Prob>|t|
Intercept 0.1179286 0.006255 18.85 <.0001
A 0.02975 0.004584 6.49 0.0013
NLS 8.327e-17 0.004584 0.00 1.0000
(A-0.5)*(NLS-0.5) -8.67e-18 0.009168 -0.00 1.0000
B 0.04025 0.004584 8.78 0.0003
(A-0.5)*(B-0.5) 0.0165 0.009168 1.80 0.1318
(NLS-0.5)*(B-0.5) 1.735e-18 0.009168 0.00 1.0000
DFT -0.001879 0.000131 -14.34 <.0001
(A-0.5)*(DFT-32.5) -0.001471 0.000262 -5.62 0.0025
(NLS-0.5)*(DFT-32.5) -1.74e-17 0.000262 -0.00 1.0000
(B-0.5)*(DFT-32.5) -0.001729 0.000262 -6.60 0.0012
Influence of NLS (Novel Light Stabilizer)
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Novel Light StabilizerThe correlation between concentration and
film thickness
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w% DFT(μm ) 365nm(T%) 380nm(T%) △Y
0 10 82.5 89 6.5
0 30 71 81.3 7.6
0 50 68.4 79.2 8.4
0 140 52.3 62.1 12.4
1 10 68.7 80.5 3.1
1 30 39 62.5 4.5
1 50 33.5 57.4 5.4
1 140 2.89 19.2 6.7
3 10 50.2 74 1.8
3 30 12 37.1 2.5
3 50 7.86 33 3.2
3 140 1.67 18 3.7
5 10 24.6 55.1 0.8
5 30 6.7 31.6 1.3
5 50 0.7 11.5 1.9
5 140 0.09 6.88 2.2
Two Factors:
NLS2(w%)、DFT (μm )
w% 0 1 3 5
DFT(μm) 10 30 50 140
Test Model :340nm Light on for 120hrs
Four Levels:
Coated on glass
From the table above, the 5% concentration and 140μm DFT gives the strongest UV-filtration, but the 5% concentration with 10 μm DFT gives the best yellowing color change.
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%9.2012974
2.10512813
%5.6212974
2.10518218
T
EDFTDFTDFT
T
ENLSNLSNLS
SS
MSSS
SS
MSSS
Influence of NLS(w%) with DFT in 365nm
At 365nm, the influence on the concentration of NLS is more important than film thickness.
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%4.2711351
9913213
%7.4711351
9915509
T
EDFTDFTDFT
T
ENLSNLSNLS
SS
MSSS
SS
MSSS
Influence of NLS(w%) with DFT in 380nm
At 380nm, the influence on the concentration of NLS is more important than film thickness.
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%7.74.148
559.0109.12
%8.764.148
559.0157.114
T
EDFTDFTDFT
T
ENLSNLSNLS
SS
MSSS
SS
MSSS
Influence of NLS(w%) with DFT in Yellowness
At yellowness , the influence on the concentration of NLS is more important than film thickness.
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Combining 3 factors in 120hrs weathering study (Optimal Prediction Profilerer)
The optimal combination is 5% conc. In 140μm DFT as the best result.
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Response surface methodology (RSM) (NLS vs. DFT vs. 365nm)
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Response surface methodology (RSM) (NLS vs. DFT vs. 380nm)
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Response surface methodology (RSM) (NLS vs. DFT vs. ΔY)
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Enhanced Color Retention of Waterborne UV-Curable Clear Coatings
0 1 2 3 4 5 6 7 8
Delta Yellowness Index (△YI)
Blank
1% NLS
3% NLS
Resin:Waterborne UV-curable clear coatingExposure Time : 120 hours Test Methods :ASTM G154-1 (Q-U-V with UVB-340 light bulb)
After Test
Before Test3% NLSBlank
ΔY=7.5 ΔY=1.8
Dosage:
NLS is 1% and 3% on solid content
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Conclusions
1. For WUVA, the effect factor of curing energy is about 10.1%.
2. For WHALS, the effect factor for curing energy is about 18.6% and it’s higher than UVA.
3. For NLS, the effect of curing energy was about 0%
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Conclusions
4. NLS can be used directly and homogenously disperses very well in waterborne UV curable coating.
5. Test data showed that NLS in the waterborne clear UV curable coating did not influence with curing speed.
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